The fabrication and application of nanofiber ribbons and sheets and twisted and non-twisted nanofiber yarns

This research was supported by the Defense Advanced Research Planning Agency / Army Research Office Grant W911NF-04-1-0174, Texas High Tech Grant 009741-0130-2003, and the Robert A. Welch Foundation.

Cross-reference of related applications This patent application claims priority to the following US provisional patent applications: 60 / 626,314, filed November 9, 2004; 60 / 666,351, filed March 30, 2005; and 60 / 702,444, July 2005. Filed on the 26th.

Field of invention Methods or devices for spinning high-performance twisted, false-twisted and untwisted yarns containing nanofibers, and methods or devices for pulling out sheets and ribbons containing nanofibers are described. Molded articles, composites and applications are described for these threads, ribbons and sheets.

Explanation of background technology Single-walled carbon nanotubes (SWNTs) and multi-walled carbon nanotubes (MWNTs) are made as soot-like materials by commercial synthetic methods. It is well known that the strength and elastic modulus of the individual carbon nanotubes in this soot are extremely high, which are ~ 37 GPa and ~ 0.64 TPa, respectively, for SWNTs having a diameter of about 1.4 nm (Non-Patent Document 1). ). For applications that are lightweight but require strength, the modulus and strength normalized by the density of the individual SWNTs are even more striking, ~ 19 and ~ 54, respectively, compared to high tensile strength steel wires. high.

A significant problem hindering the application of these and other nanofibers is the lack of methods for assembling these nanofibers into long threads, sheets and molded products that effectively utilize the properties of the nanofibers. Since such nanofibers are endowed with functionality in addition to their mechanical properties, there is a lack of ways to enhance the mechanical properties of fibers made of nanofibers without compromising these other functionality. Important examples of these other functionalities that make fibers multifunctional in combination with mechanical properties are electrochromism, electrical and thermal conductivity, electromechanical operation, and electrical energy storage.

A method of growing single-walled and multi-walled nanotubes like a forest aligned in a parallel state on a solid substrate and utilizing the MWNT forest to manufacture a nanofiber assembly is known (Non-Patent Document 2). ; And Patent Document 1 (March 18, 2004). However, the resulting assembly is extremely weak and cannot be used in applications where even the slightest significant level of tensile strength is required.

Advances have been made in spinning polymer solutions or melts containing either SWNTs or MWNTs, but if the nanotube content is greater than 10%, the melt viscosity is too high for normal melt or solution spinning. Can't. Nevertheless, impressive mechanical properties are obtained for polymer solution spinning SWNTs, most of which are attributed to the mechanical properties of nanotubes (see Non-Patent Documents 3 and 4). Another problem with polymer melting and polymer solution spinning is that the nanotubes are not present in the polymer in sufficient amounts to effectively contribute to properties such as thermal and electrical conductivity. In addition, since the main component of the fiber is by far the polymer, the unique mechanical properties of the individual nanotubes are diluted.

Lobovsky et al. (Patent Document 2) described seascore melt spinning attempted to avoid the usual constraints due to the low concentration of carbon nanotubes in melt spun yarn. This method involves 30% by weight of melt mixing of very large diameter carbon MWNTs (150-200 nm in diameter and 50-100 μ in length) in a polypropylene matrix. This nanotube / polymer matrix mixture was successfully spun as a sheath / core polymer sheath containing polypropylene as the core. Despite the high viscosity of the nanotube / polymer mixture in the sheath and the brittleness of the solidified composition, the presence of the polymer core allowed this seascore spinning and subsequent partial alignment of the nanotubes in the sheath. Pyrolysis of the polypropylene left hollow (0.0115 inch outer diameter and 0.0084 inch inner diameter) nanotube threads. It was coated with carbon using a chemical vapor deposition (CVD) treatment to increase the strength of the hollow nanotube threads. Even after this CVD coating process, the hollow nanotube threads were low strength, low modulus, and fairly brittle (see Patent Document 2 by Lobovsky et al.).

The gel-based method allows continuous fibers of SWNT / poly (vinyl alcohol) compositions to be spun (Non-Patent Document 5; Non-Patent Document 6; Non-Patent Document 7; A. Lobovsky, J. Matrunich, M. Kozlov, RC Morris, and RH Baughman, Patent Document 2; and Non-Patent Document 8). The current problem with this method is that the nanotubes are combined with poly (vinyl alcohol) (PVA) and simultaneously assembled to form gel fibers and converted into solid nanotubes / PVA fibers. This PVA prevents electrical and thermal contact between the carbon nanotubes. PVA is removed by thermal decomposition, which severely degrades the mechanical properties of the fiber.

Unfortunately, the polymer-containing fibers made by the gel spinning method described above are as electrodes immersed in a liquid electrolyte because they swell dramatically (more than 100%) and lose the modulus and strength they had when dried. It is not useful for the purpose of. This method means that these polymer-containing fibers are not useful for critical applications using liquid electrolytes, such as in supercapacitors and electromechanical actuators (Non-Patent Document 6).

In another method (VA Davis et al., Patent Document 3), SWMT was first dispersed in 100% sulfuric acid and then spun into a coagulation bath of diethyl ether. Although it has high electrical conductivity (Non-Patent Document 9), the properties of the produced yarn are impaired due in part to the partial deterioration of SWNTs caused by long-term contact with sulfuric acid. This deterioration is partially remedied by high temperature thermal annealing in vacuum, but poses a serious hindrance to practical use. Furthermore, any solution-based or melt-based processing method that directly forms the polymer assembly has a length due to the increased viscosity associated with the polymer dispersion and the formation of globules with little nanotube orientation as a result of the wrapping of the nanotubes. Limited to short nanotubes (typically a few microns).

Non-Patent Document 10 reported that MWNT yarns can be formed directly from unoriented carbon nanotube airgels during nanotube synthesis by CVD. Although the plyed yarn is shown in the photograph, the ratio of nanotube length (~ 30 μm) to yarn diameter is approximately uniform, which means that significant property enhancements based on the lateral stresses generated by the plyed yarn were not obtained.

Twisting micrometer-diameter fibers to create twisted yarns with enhanced mechanical properties is well known in the art and has been widely practiced for thousands of years. However, no successful means have been devised in the prior art to achieve the potential gain of the plying for nanofibers that are more than 1000 times smaller in diameter than the prior art plying. There are about hundreds of thousands of individual nanofibers in the cross section of a 5 μm diameter yarn, compared to the 40-100 fibers in the cross section of a typical commercial wool and cotton yarn. Assembling a huge number of nanofibers to produce a twisted yarn with useful properties as a result of twisting is a huge challenge, and according to the teachings of the present invention, the structural features to be achieved and the achievement thereof. How to do it is described.

Reflecting on these issues with the prior art of nanofiber yarns, for example, carbon nanotube artificial muscles (Non-Patent Documents 11 and 4), carbon nanotube yarn superconductors, composite compositions with carbon nanotubes, and tough and advanced It can be seen that important applications such as electronic fabrics with conductive nanofiber yarns have not yet become commercially available.

While said nanotube sheets will be very beneficial for a variety of applications, prior art methods for the continuous production of durable nanotube ribbons and sheets without polymers or other binders have yet to be developed. .. Prior art carbon nanotube sheets typically use a variant of the old papermaking technique to filter nanotubes dispersed in water for a week and then remove dried nanotubes as a layer from the filter. Manufactured by peeling (see Non-Patent Document 12 and Non-Patent Document 13). An interesting variant of the filtration technique provides a highly transparent and highly conductive ultrathin nanotube sheet (see Non-Patent Documents 14 and 15). Sheets produced by the filtration method are usually isotropic in the plane of the sheet, but the result of applying a high magnetic field during the filtration period (Non-Patent Document 16), and nanotubes trapped perpendicular to the holes of the filter. Mechanical friction (Non-Patent Document 17) gives a sheet in which nanotubes are partially aligned. In other advances, nanotube sheets of weak or unreported strength are cast from unoriented airgels (Non-Patent Document 10), by Langmüller Brodget deposition (Non-Patent Document 18), and from oleum. Manufactured by (Non-Patent Document 19) and spin coating (Non-Patent Document 20).

For electronic device applications, nanofiber sheets are required to combine transparency, electrical conductivity, flexibility, and strength. Application needs include, for example, light emitting diodes (LEDs), photovoltaic batteries, flat panel liquid crystal displays, "smart" windows, electrochromic camouflage, and related applications.

Ekios has developed a transparent conductive coating agent based on carbon nanotubes (PJ Glatkowski and AJ David, Patent Document 5 (2004)). They used a solution-based technique involving carbon single-walled nanotube inks. A transparent carbon nanotube (CNT) film having a polymer binder was produced by N. Saran et al. Using a solution deposition method (Non-Patent Document 21). Similarly, transparent SWNT electrodes were manufactured by AGRinzler and Z. Chen (Patent Document 6). AGRinzler focused on the high transmittance of SWNT films in the visible and near infrared (NIR) regions (3-5 μm) (AGRinzler and Z. Chen, transparent electrodes from single-walled carbon nanotubes, Patent Document 6). )).

All of these processing methods are liquid-based and do not provide durable, transparent nanofiber electrode materials or those that may be transparent and self-supporting. Similarly, these methods do not provide nanotube-based electrodes with useful in-plane anisotropic properties such as anisotropic electrical and thermal conductivity and polarization performance.

There is a report on a successful example of using an opaque carbon nanotube film as a counter electrode of a Graeetzel photoelectrochemical battery using an electrolyte of either a liquid phase or a solid phase (see Non-Patent Document 22; and Non-Patent Document 23). ). However, durable, transparent nanofiber electrodes have not been available in dye-sensitized solar batteries (DSCs), despite the obvious requirements for them (more specifically, the requirements for flexible solid-state DSCs).

In addition, all of the above approaches are charge collection or injection from such transparent CNT coatings into organic electronic devices such as organic light emitting diodes (OLEDs), optical field effect transistors (OFETs), and solar cells. The problem was not addressed. This problem requires a very low work function (wf) for electron injection or a high work function for hole injection.

Nanofibers, and in particular carbon nanofibers, are well known to be useful as field emission sources for flat panel displays, lamps, gas discharge tubes with surge protection, and X-ray or microwave generators (non-patents). Patent Document 24; Non-Patent Document 25; Non-Patent Document 26; Non-Patent Document 27; Non-Patent Document 28; and Non-Patent Document 29). The potential applied between the carbon nanotube-containing electrode and the anode creates a high local electric field as a result of the small radius of the nanofiber tip and the small length of the nanofiber. These local electric fields cause the tunneling of electrons from the tips of the nanotubes into the vacuum. The electric field directs field-emission electrons toward the anode, where the selected fluorophore emits light for flat-panel display applications that collides with metal targets (at higher voltages) for X-ray tubes. An X-ray is emitted.

There are known methods of producing both single-walled and multi-walled carbon nanotubes as a forest of fibers aligned in parallel on a solid substrate and utilizing such an nanotube forest as a cathode (Non-Patent Document 30 and Non-Patent Document 30). Patent Document 31). However, the resulting forest assembly results in various instabilities at high current loads, one of which is the flash evaporation of catalyst and carbon, followed by the emission of light and sparks of light. There is a transfer of CNTs from the cathode to the anode, which damages the cathode (functional carbon nanotubes edited by R. Nanjundaswamy et al., D. Carroll et al. (Non-Patent Document 32)). Although advances have been made to create robust forest-oriented CNTs on glass substrates, such forests are not yet the best solution for nanofiber cold cathodes.

One of the most challenging issues with oriented CNT sequences is emission heterogeneity. Due to the effectiveness of the screening and the variation of the CNT structure and the non-uniformity of the whole sample, only a very small fraction of CNTs emit light at all times. Therefore, if no special treatment (eg, chemical or plasma) is performed, the luminescence from such a CNT forest cathode is often dominated by edge luminescence and hotspots (Non-Patent Document 33).

Stability is the second major open technical issue. Two main reasons are the cause of luminescence instability: adsorption of residual gas molecules and Joule heating of CNTs (Non-Patent Document 34, Non-Patent Document 35). Other methods of producing cold cathodes from CNTs include forming a composite with a polymeric binder (Non-Patent Document 36), where the CNTs are not oriented. Nevertheless, impressive luminescence properties were obtained for the polymeric binder / SWNT cold cathode. The field screening effect does not appear to play a decisive role in the random orientation of CNTs with a simple statistical distribution. Further, in these types of illuminants, it is possible to perform an electric field-induced alignment that significantly enhances the field emission characteristics. However, the same problems that exist for CNT orientation forests also exist for this type of emitter. The problem with polymer binders / CNT cathodes is that the nanotubes are not present in the polymer in sufficient quantity to effectively contribute to field electron emission and similar properties such as thermal and electrical conductivity. (As a result, the binder is damaged by heat and current). In addition, since the main component of the cathode is by far the polymer binder, the unique electrical properties of the individual nanotubes are weakened. Therefore, the upper level of the stable field emission current is significantly reduced. The decisive problem that prevents the application of these carbon nanotubes (CNTs) to cold cathodes is the framework of a macroscopic on-board system that is properly shaped and strong enough to effectively utilize the field emission characteristics of CNTs. There is a requirement for a method of assembling these nanotubes in.

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<p num="0027"> Abstract of the invention The present invention relates to a nanofiber yarn, and targets a method for producing the yarn and an application of the yarn. An additional embodiment provides pulling out a nanofiber ribbon, as well as a sheet having a width of any size. Importantly, this yarn spinning technique as well as sheet and ribbon drawing techniques span the production of threads, sheets and ribbons of various nanofiber materials for use in a variety of applications and devices.</p><p num="0028"> In some embodiments, the methods of the invention for spinning yarns containing nanofibers are: (a) aligned nanofibers, and (ii) focused towards alignment and of the alignment axis. A step of placing in an array selected from a group consisting of sequences that provide a major assembly in which twisting can occur; (b) a step of twisting around the alignment axis of the major assembly to produce a plyed yarn; and ( c) The plying is collected by a technique selected from the group consisting of (i) winding on a spindle, (ii) depositing on a substrate, and (iii) incorporating into another structure. In a way that includes steps; (i) The important components of the nanofibers have a maximum thickness of less than about 500 nm in the direction perpendicular to the nanofiber axis, (ii) the nanofibers are at least about 100 in the thinnest lateral thickness direction. Has a minimum length-to-thickness ratio of, (iii) a minimum ratio of nanofiber length to the circumference of the thread is greater than about 5, and (iv) a net introduced in one direction per length of thread. The twists are offset by twists in the opposite direction, with at least about 0.06 / D turns for twisted yarns of diameter D. In some embodiments, the placement step involves a withdrawal process.</p><p num="0029"> The unidirectional twisting of the single yarn before or after yarn collection is offset by the opposite twisting at another stage in processing for various useful purposes. For example, (a) folding the yarn itself and twisting the yarn, (b) forming a composite or fused structure in which the nanotubes are untwisted or twisted at the lowest level. Is. The advantage of the early introduced twist allows the yarn to be densified and / or strengthened to give the yarn more force during the initial process.</p><p num="0030"> In some embodiments, the present invention relates to a method of producing a thread containing nanofibers, which method: (a) provides a preliminary main assembly comprising an array of substantially parallel nanofibers; (b). A step of pulling out of a preliminary main assembly to give a main assembly of nanofibers with an alignment axis that twists around, where the main assembly is (i) aligned, (ii) aligned around the alignment axis. Selected from a group consisting of sequences that focus towards; and (c) a method that includes twisting around the alignment axis of the main assembly to produce the twisted yarn.</p><p num="0031"> In some embodiments, the present invention relates to a device for producing a thread containing nanofibers, which device (a) provides a preliminary main assembly comprising an array of substantially parallel nanofibers; b) Steps to pull out of the preliminary main assembly to provide a main assembly of nanofibers with an alignment axis that twists around, the main assembly is (i) aligned alignment, (ii) around the alignment axis. Selected from a group consisting of sequences that focus towards alignment; and (c) a step of twisting around the alignment axis of the main assembly to produce a twisted yarn, which operates to perform a method.</p><p num="0032"> In some embodiments, the present invention relates to an apparatus for producing a thread containing nanofibers, wherein the apparatus is: (a) a preliminary main assembly comprising an array of substantially parallel nanofibers; (b) a reserve. A pull-out mechanism attached to the main assembly that operates to pull out from the preliminary main assembly to provide a main assembly of nanofibers with an alignment axis around which twists occur, and the main assembly is (i) aligned. Selected from a group consisting of the aligned sequences, (ii) sequences that focus towards alignment around the alignment axis; and (c) actuate to twist around the alignment axis of the main assembly to produce the twisted yarn. A device for producing yarns containing nanofibers, including a twisting mechanism.</p><p num="0033"> In some embodiments, the present invention relates to methods of making nanofiber ribbons or sheets and includes the following steps: (a) Substantial placement of nanofibers with some degree of fiber interconnectivity in the nanofiber arrangement. A step of providing an array of nanofibers parallel to; and (b) a step of pulling the nanofibers out of the nanofiber array as a ribbon or sheet substantially without twisting the ribbon or sheet, the ribbon or sheet. It is at least about 1 mm wide.</p><p num="0034"> In some embodiments, the present invention comprises the following steps with respect to an apparatus for producing nanofiber ribbons or sheets. The device operates to perform a method that includes the following steps: (a) Place the nanofibers and provide a substantially parallel array of nanofibers with some degree of fiber interconnectivity in the nanofiber array. And (b) the step of pulling the nanofibers out of the nanofiber array as a ribbon or sheet with virtually no twist on the ribbon or sheet, the ribbon or sheet being at least about 1 mm wide.</p><p num="0035"> In some embodiments, the present invention relates to a device for producing nanofiber ribbons or sheets: (a) a substantially parallel array of nanofibers with some degree of fiber interconnectivity in the nanofiber array; And (b) a pull-out mechanism that pulls the nanofibers out of the nanofiber array as a ribbon or sheet without substantially twisting the ribbon or sheet, the ribbon or sheet having a width of at least about 1 mm. ..</p><p num="0036"> In some embodiments, the present invention relates to a nanofiber monofilament in which at least about 10,000 nanofibers are contained within a 1 square micron cross section of the nanofiber monofilament. There is a length of at least about 1 meter; (b) nanofiber single yarns have a diameter less than about 10 microns; and (c) nanofiber single yarns are not overlapped, overlapped. A single yarn of nanofibers comprising, and a shape selected from the group consisting of combinations thereof.</p><p num="0037"> In some embodiments, the invention relates to a method comprising the following steps: (a) selecting a porous thread containing nanofibers; (b) knotting the thread to form a star thread; And (c) gas; steam; plasma; liquid; solution; fluid dispersion; supercritical liquid; substances selected from the group consisting of melts; electrochemical deposition, electrochemical material removal, electrochemical polymerization , And the steps to achieve region-selective material processing of yarns by exposing them to conditions that result in their combination.</p><p num="0038"> In some embodiments, the present invention relates to a method of producing a deformable nanofiber sheet or ribbon, the method comprising: (a) an elastically deformable substrate, an electrically deformable. A step of selecting a substrate from a group consisting of a substrate and a combination thereof; (b) a step of stretching the substrate to form a deformed substrate, wherein the elongation is elastic elongation, electrical elongation, And a combination thereof selected from the group; (c) adhesively applied to a nanofiber sheet or ribbon to form a deformed substrate; and (d) at least partial after the adhesive application step. A method of making a deformable nanofiber sheet or ribbon, comprising the step of allowing the stretch to return.</p><p num="0039"> In some embodiments, the present invention relates to a method of implanting an elastically deformable nanofiber sheet between two elastomeric polymer sheets: (a) selecting the first elastomeric polymer sheet. (B) Elastically stretching the first elastomer polymer sheet to form a deformed substrate; (c) Adhesive application of the nanofiber sheet to the deformed substrate; (d) After the adhesive application step Allowing the return of the elastic elongation at least partially; (e) When the first elastomer polymer sheet is relaxed or partially relaxed, the nanofiber sheet is subjected to the second elastomer polymer. Applying a resin precursor for the sheet; and (f) curing the resin precursor to form a second elastomer polymer sheet while the first elastomer polymer sheet is in a relaxed or partially relaxed state. This is a method of embedding an elastically deformable nanofiber sheet.</p><p num="0040"> In some embodiments, the present invention relates to a method of spinning a thread containing nanofibers, (a) a step of withdrawing a major assembly containing aligned nanofibers from a nanofiber forest, in the drawing direction and in the forest. The angle between the fiber alignment directions is between about 90 ° and about 5 ° with the step; and (b) the main assembly of the nanofibers is twisted around the axis that is roughly aligned with the nanofibers of the main assembly. It is a method of spinning a yarn containing nanofibers, which comprises a step of producing a twisted yarn of nanofibers.</p><p num="0041"> In some embodiments, the present invention relates to a method of spinning a thread containing nanofibers, (a) drawing from an arrangement as a synthesized nanofiber to form a major assembly containing a plurality of substantially aligned nanofibers. The steps in which the nanofibers from the nanofiber array are continuously linked during the withdrawal step, maintain the connection of the previous withdrawal step during the withdrawal step, or a combination thereof. Steps; and (b) The step of twisting the main assembly of aligned nanofibers around a substantially aligned shaft to produce a twisted fiber, the length of the main nanofiber being the circumference of the nanofiber twisted yarn. A method of spinning yarn, including at least five times as many steps.</p><p num="0042"> In some embodiments, the present invention relates to a method of producing a plying yarn containing nanofibers, the method comprising: (a) containing at least 20% by weight of nanofibers using a liquid-based method. A method of producing a twisted yarn containing nanofibers, comprising the step of twisting the nanofiber yarn; and (b) the step of twisting around the direction of the yarn to give the twisted yarn.</p><p num="0043"> In some embodiments, the present invention relates to a method of producing a nanofiber ribbon or sheet from a nanofiber forest, (a) a step of producing a nanofiber forest containing nanofibers, and the nanofiber forest is a nanofiber. Suitable for pulling a ribbon or sheet at least about 1 mm wide from the forest, the nanofiber forest has side walls; (b) Steps to connect the attachment to the side wall or near the side wall of the nanofiber forest; and ( c) A method of producing a nanofiber ribbon or sheet from a nanofiber forest, which comprises the step of pulling the nanofiber ribbon or sheet out of the nanofiber forest by pulling the attachment.</p><p num="0044"> In some embodiments, the present invention relates to a method comprising the following steps: ((a) A step of producing a carbon nanotube forest containing carbon nanotubes, wherein the carbon nanotube forest is a ribbon from the carbon nanotube forest. Or suitable for pulling out the tube, the ribbon or sheet is at least about 1 mm wide, and the carbon nanotube forest has side walls; (b) Steps to connect the attachment to the side wall or near the side wall of the carbon nanotube forest. (C) The step of pulling the ribbon or sheet out of the carbon nanotube forest by utilizing the attachment, where the ribbon or sheet is a highly oriented airgel ribbon or sheet; and (d) The sheet or ribbon The step of infiltrating with a liquid and then evaporating the liquid from the sheet or ribbon, the infiltration and evaporation is a method including at least partially densifying the sheet or ribbon to form a densified sheet or ribbon. ..</p><p num="0045"> In some embodiments, the present invention relates to a method of strengthening a yarn, ribbon, or sheet containing nanofibers, (a) a step of infiltrating a liquid into the yarn, ribbon or sheet; and (b) the yarn, ribbon. Alternatively, a method of strengthening a thread, ribbon, or sheet, comprising evaporating a liquid from the sheet to strengthen the thread, ribbon, or sheet.</p><p num="0046"> In some embodiments, the present invention relates to a method of strengthening a yarn containing nanofibers, (a) a step of twisting in a first direction; (b) a step of twisting in a second direction, second. Is a method of strengthening a yarn containing nanofibers, including a step in which the direction of is opposite to that of the first direction and the net twist of the plying in the first and second directions is about zero.</p><p num="0047"> In some embodiments, the present invention relates to devices for producing nanofiber twisted yarns: (a) nanofiber feeders; (b) transport tubes for transporting nanofibers from supply to collector; (c). ) A rotatable collector that collects nanofibers from the supply; and (d) a winder that collects nanofiber twisted yarn from the collector while the collector is rotated, so that the twisted nanofiber yarn comes from the collector. The nanofibers inside the collector as they are recovered are devices for producing nanofiber twisted yarns, including winders that are twisted to form nanofiber twisted yarns.</p><p num="0048"> In some embodiments, the present invention relates to methods of making nanofiber strands: (a) continuously feeding nanofibers to collectors; (b) to form generally parallel nanofiber assemblies. The step of rotating the collector; (c) the step of forming the nanofiber yarn from the assembly; and (d) the step of collecting the nanofiber yarn from the assembly, in which the yarn is twisted by the rotation of the collector to produce the nanofiber twisted yarn. It is a method of producing a nanofiber twisted yarn, which comprises a step of forming.</p><p num="0049"> In some embodiments, the present invention relates to an apparatus for producing nanofiber strands, the apparatus operating to perform a method comprising the following steps: (a) feeding the collector with continuous nanofibers. Steps; (b) Rotating the collector to form a generally parallel nanofiber assembly; (c) Forming nanofiber threads from the assembly; and (d) Retrieving nanofiber threads from the assembly It is a device for manufacturing nanofiber twisted yarns, which includes a step of recovering nanofiber yarns from an assembly.</p><p num="0050"> In some embodiments, the present invention relates to a device comprising an array of aligned conductive channels: (a) the conductive channel is a type selected from the group consisting of electrons, ions, phonons, and combinations thereof. Can be manipulated to directionally transport; and (b) the conductive channels are provided by nanofibers in a form selected from the group consisting of ribbons, sheets, threads and combinations thereof, including adjustments. A device that contains an array of conductive channels.</p><p num="0051"> In some embodiments, the present invention relates to methods comprising the following steps: (a) providing oriented nanofibers in a form selected from the group consisting of ribbons, sheets, threads and combinations thereof; and (b). ) A method comprising the step of using the oriented nanofibers as an array of conductive channels for directional transport of a type selected from groups consisting of electrons, ions, phonons and combinations thereof.</p><p num="0052"> In some embodiments, the present invention relates to devices including: (a) cathodes containing nanofibers in a form selected from the group consisting of threads, ribbons, sheets and combinations thereof; and (b) low gas pressure. Region is a device that includes an anode that separates from the cathode.</p><p num="0053"> In some embodiments, the present invention relates to devices including: (a) cold cathodes for field emission containing nanofibers of a shape selected from the group consisting of threads, ribbons, sheets and combinations thereof. The steps of arranging the nanofibers, the shape of which is (i) aligned in an array with sufficient interfiber connectivity in the array, to provide the main assembly, and (ii) as the electrode material from the main assembly. The device is manufactured by a method comprising pulling out the nanofibers; and (b) an anode in which a region of low gas pressure separates from the cathode.</p><p num="0054"> A method of patterning nanofiber sheets along their length, which includes photopolymerization, photolithography, electron beam-induced polymer reactions, pressure-induced mass transfer, material deposition, removal, and deformation. A method comprising a patterning technique selected from the group consisting of liquid, gas phase, and plasma treatments, and combinations thereof.</p><p num="0055"> In some embodiments, the present invention relates to an optoelectronic device, which is: (a) a first electrode, a form of nanofiber selected from the group consisting of threads, ribbons, sheets, and combinations thereof. Containing; (b) an active layer that can be operated in cooperation with the first electrode; and (c) an optoelectronic device that includes an active layer and a second electrode that can be operated in cooperation with the first electrode.</p><p num="0056"> In some embodiments, the present invention relates to an optoelectronic device, which comprises: (a) a first electrode, a form of nanofiber selected from the group consisting of ribbons, sheets, and combinations thereof. The steps of arranging the nanofibers in an aligned array with sufficient interfiber interconnection within the array so that the shape (i) provides the main assembly; and (ii) the nanofibers as electrode material from the main assembly. First electrode manufactured by a method that includes a step of pulling out; (b) an active layer that can be operated in cooperation with the first electrode; and (c) a second that can be operated in cooperation with the active layer and the first electrode. It is an optoelectronic device including an electrode.</p><p num="0057"> In some embodiments, the present invention relates to a method of manufacturing an optoelectronic device, which method comprises: (a) providing components including: (i) operably used as a first electrode. A self-supporting nanofiber material to be made, said material in a form selected from the group consisting of threads, ribbons, sheets and combinations thereof, and the material is about 100 m.²/ g and 300m²It has a three-dimensional network pore with a surface area in the range between / g; (ii) an active material layer operably associated with the first electrode; and (iii) operable with the active material and the first electrode. A method of manufacturing an optoelectronic device that includes an associated second electrode; and (b) a step of assembling components to form the optoelectronic device operably.</p><p num="0058"> In some examples, the nanotube thread comprises carbon nanotubes. Such carbon nanotubes of the present invention provide unique and combinatorial properties such as: extreme toughness, break resistance at knots, high levels of electrical and thermal conductivity, reversibly. High energy absorption to emerge, break strain up to 13% compared to a few percent break strain in other fibers with similar toughness, very high creep resistance, 1 in ~ 450 ° C in air It retains its strength when heated for hours, and has very high radiation resistance and UV resistance even when irradiated in air. In addition, these nanotube yarns can be spun as yarns with a diameter of 1 micron and optionally twisted to form twin yarns, quadruple yarns, and polycot yarns to form linear densities (ie, per unit length of yarn). Weight) can be increased.</p><p num="0059"> In some embodiments, the nanofibers are nanoscrolls. In some embodiments, the nanofibers are chemically and / or physically modified before or after twisting or twisting or withdrawal of the ribbon or sheet. In some embodiments, nanofiber yarns are used to form composites.</p><p num="0060"> The nanofiber yarns of the present invention are used in a wide variety of applications. In some embodiments, the spinning technique extends to the production of nanofibers of various nanofibers and nanoribbons of various materials and can extend the range of applications. The nanofiber yarn applications of the present invention include textiles; electronic devices; conductive wires or cables; electrochemical devices such as fiber-based supercapacitors; batteries; fuel cells; artificial muscles; and electrochromic products; electroemission and Incandescent light emitting devices; protective clothing; tissue scaffolding applications; and mechanical and chemical sensors.</p><p num="0061"> The advantages of the present invention will be further clarified by the following detailed description. However, detailed description and specific examples are given for illustration purposes only, showing preferred embodiments of the present invention. This detailed description will reveal to engineers in the art a variety of modifications and modifications within the scope of the gist and application of the present invention. For example, the present invention provides the following items. (Item 1) A method of producing yarn containing nanofibers. (a) With the step of providing a preliminary main assembly containing a substantially parallel array of nanofibers, (B) A step of withdrawing from a preliminary main assembly to provide a main assembly of nanofibers with an alignment axis on which twists can occur, wherein the main assembly is (i) an aligned arrangement, and (ii) said. Steps, which are the main assemblies selected from the group consisting of arrays that focus towards alignment around the alignment axis. (c) A method comprising a step of twisting around an alignment axis of the main assembly to produce a twisted yarn. (Item 2) A device for manufacturing yarns containing nanofibers. (a) With the step of providing a preliminary main assembly containing a substantially parallel array of nanofibers, (B) A step of withdrawing from a preliminary main assembly to provide a main assembly of nanofibers with an alignment axis on which twists can occur, wherein the main assembly is (i) an aligned arrangement, and (ii) said. Steps, which are the main assemblies selected from the group consisting of arrays that focus towards alignment around the alignment axis. (c) A device that can be actuated to perform a method comprising stepping into a step of twisting around the alignment axis of the main assembly to manufacture the twisted yarn. (Item 3) A device for manufacturing yarns containing nanofibers. (a) With a preliminary main assembly containing a substantially parallel array of nanofibers, (b) A pull-out mechanism attached to the preliminary main assembly, which can be actuated to pull out from the preliminary main assembly to provide a main assembly of nanofibers with an alignment axis on which twists can occur. The withdrawal mechanism, wherein the main assembly is the main assembly selected from a group consisting of (i) aligned sequences and (ii) sequences focused towards alignment around the alignment axis. (c) A device comprising a plying mechanism that is capable of operating to twist around an alignment axis of said main assembly to produce a plying. (Item 4) The method of item 1 or the apparatus of item 2 or 3, wherein the nanofibers are chemically synthesized to form a substantially parallel array of nanofibers. (Item 5) The method of item 1 or the device of item 2 or 3 where the preliminary main assembly is not a nanofiber yarn. (Item 6) The method of item 1 or the device of item 2 or 3 in which the orientation direction of the preliminary main assembly is different from the orientation direction of the main assembly. (Item 7) The method of item 1 or the apparatus of item 2, wherein the step of providing the preliminary main assembly does not include forming the preliminary main assembly by a mechanical withdrawal method. (Item 8) The method of item 1 or the device of item 2 or 3, wherein the drawer from the preliminary main assembly for manufacturing the main assembly removes only a part of the nanofibers from the preliminary main assembly. (Item 9) Item 8. The method or apparatus of item 8, wherein the portion is used to produce a single twisted yarn and the portion is less than 10% of the nanofibers in the preliminary assembly. (Item 10) The method of item 1 or the apparatus of item 2 wherein the provision of the preliminary assembly comprises forming the preliminary assembly by dispersing the nanofibers in a liquid. (Item 11) The twisted yarn is collected by a technique selected from the group consisting of (a) winding the twisted yarn around a spindle, (b) depositing the twisted yarn on a substrate, and (c) incorporating the twisted yarn into another structure. Item 1 method or item 2 device, including further methods. (Item 12) The device of item 3, further comprising means for collecting the twisted yarn, selected from the group consisting of spindles, substrates, structures, and combinations thereof. (Item 13) The method of item 1 or the device of item 2 or 3 in which an important component of the nanofiber has a maximum thickness of up to about 500 nm orthogonal to the nanofiber axis. (Item 14) The method of item 1 or the device of item 2 or 3 in which the nanofibers have a minimum length-to-thickness ratio of at least about 100 in the thinnest lateral thickness direction. (Item 15) The method of item 1 or the device of item 2 or 3 where the minimum ratio of nanofiber length to the circumference of the twisted yarn is at least about 5. (Item 16) The method of item 1 or the device of item 2 or 3 where the maximum twist introduced in one direction per twist length is at least about 0.06 / D turn for a twist having a diameter D. (Item 17) (a) An important component of the nanofiber has a maximum thickness of up to about 341 nm orthogonal to the nanofiber axis. (b) Nanofibers have a minimum length-to-thickness ratio of at least about 100 in the thinnest lateral thickness direction. (c) The minimum ratio of nanofiber length to circumference of the twisted yarn is at least about 5 and (d) The method of item 1 or the device of item 2 or 3 where the maximum twist introduced in one direction per twist length is at least about 0.06 / D turn for a twist having a diameter D. (Item 18) The method or device of item 16 or 17, where the maximum twist introduced in one direction is at least about 0.12 / D turns. (Item 19) The method or device of item 16 or 17, where the maximum twist introduced in one direction is at least about 0.18 / D turns. (Item 20) The method or device of item 16 or 17, where the maximum twist introduced in one direction is between about 0.06 / D turns and about 0.18 / D. (Item 21) The method or apparatus of item 13 or 17, wherein the maximum thickness orthogonal to the nanofiber axis of the important component of the nanofiber is up to about 100 nm. (Item 22) The method or apparatus of item 13 or 17, wherein the maximum thickness orthogonal to the nanofiber axis of the key component of the nanofiber is up to about 30 nm. (Item 23) The method of item 13 or 17, wherein the nanofibers are at least approximately columnar such that the maximum thickness of the key components of the nanofibers orthogonal to the nanofiber length direction is at least the approximate diameter of the nanofibers. apparatus. (Item 24) The method or apparatus of item 14 or 17, wherein in the direction of the thinnest lateral thickness of the nanofibers, the minimum length-to-thickness ratio is at least about 1000. (Item 25) The method or apparatus of item 14 or 17, wherein the majority weight fraction of nanofibers has a minimum ratio of length to thickness of at least 50 in the thinnest lateral thickness direction. (Item 26) The method or apparatus of item 15 or 17, wherein the nanofibers in the twisted yarn have a minimum ratio of at least about 10 of the nanofiber length to the twisted yarn circumference. (Item 27) The method of item 1 or the device of item 2 or 3 where the twisted yarn has a weight average nanofiber length of at least twice the length of one turn of twisting of the twisted yarn. (Item 28) The method of item 1, wherein the major weight fraction of the nanofibers in the twisted yarn at a distance from near the surface of the twisted yarn to deep inside the twisted yarn and back to near the surface of the twisted yarn is up to about 20% of the nanofiber length. Or the device of item 2 or 3. (Item 29) Item 1 method or item 2 or 3 equipment in which the preliminary main assembly is a nanofiber forest. (Item 30) Item 1 method or item 2 or 3 device in which the preliminary main assembly is a carbon nanotube forest. (Item 31) Item 30 method or apparatus in which the strands are essentially formed of carbon nanotubes from the forest that are simultaneously drawn from the entire forest height. (Item 32) The method or apparatus of item 30, wherein the carbon nanotubes are multi-walled carbon nanotubes having a diameter of about 10 nm. (Item 33) Forest density at the base of the forest is at least 20 billion nanotubes / cm²Item 30 method or device. (Item 34) The method or apparatus of item 33, wherein the percentage of the area of the base of the forest occupied by carbon nanotubes is higher than about 4%. (Item 35) The method or apparatus of item 34, wherein the area of the base of the forest occupied by carbon nanotubes is less than about 40%. (Item 36) When measured at the base of the forest, the product of (i) the number of carbon nanotubes per unit area in the forest and (ii) the diameter of the carbon nanotubes is in the range between 0.16 and 1.6, item 30. Method or device. (Item 37) Item 30 method or device in which carbon nanotubes in the forest are intermittently bundled. (Item 38) Item 30 method or apparatus in which at least about 20% of carbon nanotubes initiated in the base region of the forest extend essentially to the top of the forest. (Item 39) Item 30 method or equipment in which the height of the forest is at least about 50 microns. (Item 40) Item 30 method or equipment in which the height of the forest is at least about 100 microns. (Item 41) The method of item 1 or the apparatus of item 2 or 3, wherein the main assembly has an end and the main assembly is twisted directly around the end to produce a ply. (Item 42) The method of item 1 or the apparatus of item 2 or 3, wherein the twisted yarn has an end and the end is attached directly to a roller used to collect the twisted yarn. (Item 43) The method of item 1 or the device of item 2 or 3 in which the ply is not in contact with any intermediate surface between the start of withdrawal from the preliminary assembly and the start of the ply around the alignment axis. (Item 44) The method of item 1 or the device of item 2 or 3, wherein the rollers are used for twisting by rotation around the alignment axis of the main assembly, the rollers being rotated simultaneously around the axis of the roller for collecting the thread. (Item 45) 44. The method or apparatus of item 44, wherein the rollers have a first drive and a second drive, the first drive and the second drive operating independently and the twist in the twisted yarn being freely variable. (Item 46) Item 30 method or equipment in which the cradle is used to support the substrate on which the carbon nanotube forest grows. (Item 47) 46. The method or apparatus of item 46, wherein the cradle is arranged to hold a plurality of substrates supporting a carbon nanotube forest. (Item 48) 46. The method or apparatus of item 46, wherein the substrate has first and second surfaces and a carbon nanotube forest grows on the first and second surfaces of the substrate. (Item 49) (a) The nanofibers contain multi-walled carbon nanotubes. (b) The method of item 1 or the apparatus of item 2 or 3, wherein the twisted yarn is a multilayer carbon nanotube yarn. (Item 50) The method or device of item 49, in which the main assembly is rotated around an axis aligned with the spindle of the multi-walled carbon nanotube yarn. (Item 51) The method or apparatus of item 49, wherein the multi-walled nanotube yarn is attached to a roller that rotates about the axis of the roller for collecting the multi-walled carbon nanotube yarn. (Item 52) The method of item 1 or the apparatus of item 2 or 3, wherein the planar substrate supporting the multi-walled carbon nanotube forest is housed in a rotating holder, the rotating holder having axes substantially aligned along the axis of the strands. (Item 53) (a) Multiple flat substrates are housed in a rotating holder (b) Multiple planar substrates each support a multi-walled carbon nanotube forest, and (c) The method of item 1 or the device of item 2 or 3, wherein the rotating holder has a shaft substantially aligned along the shaft of the twisted yarn. (Item 54) 52. The method or apparatus of item 52, wherein the substrate is columnar. (Item 55) 53. The method or apparatus of item 53, wherein the plurality of flat substrates are each cylindrical. (Item 56) The method of item 1 or the device of item 2 or 3 which further comprises the step of collecting the plying by winding the plying and is utilized for the motor to perform the twisting and winding at the same time. (Item 57) 56. The method or apparatus of item 56, wherein the motor uses discs and electromagnets to simultaneously perform plying and winding. (Item 58) The motor is a single speed change motor, and the single speed change motor sets the level of plying independently of the level of winding by adjusting the speed of twisting and the speed of winding without interruption. Can item 56 method or device. (Item 59) Item 1 method or item 2 or 3 device in which the level of plying and the production rate of plying can be controlled by an electronic interface. (Item 60) Item 1 method or item 2 or 3 apparatus, wherein the produced twisted yarn is subjected to the minimum tension by the method or apparatus to produce a twisted yarn having a small breaking strength. (Item 61) The method of item 1 or the apparatus of item 2 or 3, further comprising producing a plurality of twisted yarns and spinning the plurality of twisted yarns together to produce a multi-strand yarn. (Item 62) Item 61. The method or apparatus of item 61, wherein the apparatus used to produce a plurality of twisted yarns for continuously producing a multi-strand yarn is further utilized to superimpose the plurality of twisted yarns together. (Item 63) Item 1 method or item 2 or 3 equipment in which the withdrawal and plying are performed at temperatures between about -20 ° C and about 500 ° C. (Item 64) Item 1 method or item 2 or 3 equipment in which drawing and plying are performed at temperatures up to approximately 50 ° C. (Item 65) At least one of the drawers and plying (a) Resistance heating of nanofibers by passing an electric current along the twisted yarn, (b) Absorption by nanofibers of electromagnetic wave irradiation from a region selected from the group consisting of visible light, ultraviolet light, infrared light, radio frequency, microwave frequency and combinations thereof, and (c) their combination, The method of item 1 or the device of item 2 or 3 performed in a heated state using a heating means selected from the group consisting of. (Item 66) The method of item 1 or the device of item 2 or 3 in which the preliminary primary nanofiber assembly has a nanofiber orientation that is at least approximately orthogonal to the substrate. (Item 67) 66. The method or apparatus of item 66, wherein the substrate is approximately planar. (Item 68) The method or apparatus of item 67, wherein the substrate is approximately columnar. (Item 69) The preliminary main assembly is a nanofiber forest, the nanofiber forest is supported on a non-planar substrate, and the minimum radius of curvature with respect to the occupied area of the nanofiber forest on the non-planar substrate is nanofiber. Item 1 method or item 2 or 3 equipment that is at least about 10 times the maximum forest height. (Item 70) The method or apparatus of item 66, wherein the substrate is flexible enough to be machined on rollers. (Item 71) The method or apparatus of item 66, at least approximately orthogonal orientations are provided by the nanofiber forest. (Item 72) The method of item 1 or the apparatus of item 2 or 3, wherein the nanofibers are predominantly carbon nanotubes. (Item 73) The method or apparatus of item 72, wherein the carbon nanotubes are predominantly multi-walled carbon nanotubes. (Item 74) The method or apparatus of item 72, wherein the carbon nanotubes are arranged in bundles at least partially in the carbon nanotube forest, and the individual carbon nanotubes are occasionally contained in at least one bundle. (Item 75) Item 74. The method or apparatus of item 74, wherein the partial arrangement within the bundles in the carbon nanotube forest and the movement of individual nanotubes between the bundles is achieved or enhanced by the treatment of the carbon nanotube forest. (Item 76) The method or apparatus of item 75, wherein the treatment comprises infiltration of the fluid into the carbon nanotube forest and subsequent removal of the fluid from the carbon nanotube forest. (Item 77) Including applying a thread strengthening agent (a) Additives selected from the group consisting of friction aids, electrolytes, binders, seeds that enhance the thermal conductivity of yarns, seeds that enhance the electrical conductivity of yarns, and combinations thereof. Including (b) The yarn strengthening agent is applied to at least one of the preliminary main assembly, the main assembly, and the twisted yarn. Item 1 method or item 2 or 3 method or device. (Item 78) From the group consisting of the application from the gas state, the application from the liquid state, the method by gas plasma, the electrochemical method from the solution, the method by particle infiltration, the method by fiber infiltration, and a combination thereof. Item 77 method or device applied by the method selected. (Item 79) The method or apparatus of item 77, wherein the yarn strengthening agent is applied after the production of the twisted yarn. (Item 80) The method or apparatus of item 77, wherein the yarn strengthening agent comprises a polymer. (Item 81) The method or apparatus of item 80, wherein the polymer is selected from the group consisting of polyvinyl alcohol, polyvinyl alcohol copolymers, and combinations thereof. (Item 82) The method or apparatus of item 77, wherein the yarn strengthening agent is applied while the twisted yarn is subject to tension strain. (Item 83) The method or apparatus of item 82, wherein the tensile strain is at least about 10% of the breaking strain of the twisted yarn to which the yarn strengthening agent has not been applied. (Item 84) The preliminary main assembly of the nanofibers comprises an agent selected from the group consisting of applied friction improvers, binders useful for spinning, binders useful for twist retention, and combinations thereof. Method or device of item 2 or 3. (Item 85) The main assembly and twisted yarn are at least one of the following: (a) Nanofibers with substantially different dimensions; (b) Non-nano size diameter fibers with varying degrees of dimensional homogeneity; (c) Nanofibers with various surface treatments; and (d) The method of item 1 or the device of item 2 or 3 comprising nanofibers having an effective continuous length. (Item 86) The method of item 1 or the device of item 2 or 3 in which the nanotubes in the preliminary main assembly are coated with a hydrophobic material. (Item 87) 86. The method or apparatus according to item 86, wherein the hydrophobic material comprises a fluorocarbon polymer. (Item 88) The method of item 1 or the apparatus of item 2 or 3 where a surface treatment is performed and said surface treatment is performed by a vapor phase reaction. (Item 89) The method of item 1 or the device of item 2 or 3 in which drawing and twisting are performed simultaneously to produce the plyed yarn. (Item 90) The method of item 1 or the device of item 2 or 3 in which the plying transforms the nanofiber ribbon wedge into plying. (Item 91) The method or apparatus of item 90, in which a substantially complete conversion from a nanofiber ribbon wedge to a partially twisted yarn with an approximately circular cross section occurs within approximately 5 cm of the preliminary main assembly. (Item 92) The method or apparatus of item 90, in which a substantially complete conversion from a nanofiber ribbon wedge to a partially twisted yarn with an approximately circular cross section occurs within about 5 mm of the preliminary main assembly. (Item 93) The method or apparatus of item 90, wherein the nanofiber ribbon wedge is pulled out of the nanofiber forest. (Item 94) Within distance from the nanofiber forest, the virtually complete conversion from a nanofiber ribbon wedge to a partially twisted yarn with an approximately circular cross section is up to approximately 10 times the width of the nanofiber forest. Item 93 method or device that occurs in. (Item 95) Within distance from the nanofiber forest, the virtually complete conversion from a nanofiber ribbon wedge to a partially twisted yarn with a nearly circular cross section is approximately up to about 3 times the width of the nanofiber forest. Item 93 method or device that occurs in. (Item 96) (a) The nanofiber ribbon wedge has a wedge end, a wedge apex, a first side wing and a second side wing; (b) The formation of the thread core is about 1/4 to about 3/4 of the distance from the wedge end to the wedge apex and about the lateral distance between the first and second side wings. Appears between 1/4 and about 3/4, Item 93 method or device. (Item 97) The method of item 1 or the device of item 2 or 3 comprising an aligned nanofiber array in which the main assembly is a substantially rectangular nanofiber ribbon having a width of at least 1 mm. (Item 98) Item 1 method or item 2 in which the nanofibers are selected from a group consisting of single-walled nanotubes, double-walled nanotubes, multi-walled nanotubes, scroll nanotubes, coiled nanotubes, functionalized nanotubes, deconducted nanotubes, and combinations thereof. Or 3 devices. (Item 99) (a) Infiltration of the twisted yarn with a catalyst for nanofiber growth, (b) The method of item 1 or the equipment of item 2 or 3, further comprising growing nanofibers inside the twisted yarn using chemical vapor deposition. (Item 100) Item 99. The method or apparatus according to item 99, wherein the twisted yarn contains carbon nanotubes and the nanofibers grown by chemical vapor deposition contain carbon nanotubes. (Item 101) The method or apparatus of item 99, wherein the nanofibers contain primarily carbon nanotubes on a weight basis. (Item 102) The method or apparatus of item 99, wherein the nanofibers include carbon nanotubes that are conductive on a weight basis, primarily like metals. (Item 103) The method of item 1 or the apparatus of item 2 or 3, wherein the nanofibers include carbon nanotubes having an interior that is at least partially filled with material. (Item 104) The nanofibers are imogolite nanofibers, carbon nanotubes, doped carbon nanotubes, SiC nanofibers, and MgB.₂Nanofiber, carbon-doped MgB₂Nanofibers, Bi nanofibers, binary nanofibers of Group III-V elements, Si nanofibers, ZnO nanofibers, selenium nanofibers, fluorinated nanofibers, nanofibers of compounds of Mo, S and I, and them. Item 1 method or item 2 or 3 device selected from a group consisting of combinations of. (Item 105) Preliminary main assembly is the method of item 1 or the equipment of item 2 or 3 which mainly contains multi-walled carbon nanotubes manufactured by chemical vapor deposition. (Item 106) The method of item 1 or the device of item 2 or 3 where the drawer is at a withdrawal angle between about 90 ° and about 60 ° and the withdrawal angle is the angle between the withdrawal direction and the direction of the nanofibers in the forest. .. (Item 107) The method of item 1 or the device of item 2 or 3 where the withdrawal is at a withdrawal angle between about 0 ° and about 50 ° and the withdrawal angle is between the withdrawal direction and the direction of the nanofibers in the forest. .. (Item 108) The method of item 1, wherein the preliminary main assembly comprises a nanofiber forest, wherein the nanofiber forest is stripped from a grown substrate for the forest and manufactured into a twisted yarn without adhering to the grown substrate. Or the device of item 2 or 3. (Item 109) More than one nanofiber forest is stripped from the grown substrate for the nanofiber forest and stacked on top of each other to provide an array of nanofiber forest layers from which the yarn is produced, item 1 or item 8 methods or equipment. (Item 110) The method of item 1 or the apparatus of item 2 or 3, further comprising derivatizing the end of the nanofiber near the end region of the nanofiber. (Item 111) The method or apparatus of item 110, which derivatizes the ends of nanofibers to allow nanofibers in adjacent nanofiber forests to bond at least approximately between terminals. (Item 112) (a) Forming binding aids at the interface between the arrays of stacked nanofiber forest layers, and (b) The method or apparatus of item 109, further comprising withdrawing from an array of nanofiber forest layers stacked at a local temperature that provides the fluidity of the binding aid. (Item 113) The item in which the nanofibers are synthesized on a substrate as a forest in the growth region of the furnace, and the substrate continuously moves from the growth region of the furnace to the region in which the nanofibers are drawn and twisted in the forest. Method 1 or device of item 2 or 3. (Item 114) Item 113. The method or apparatus according to item 113, wherein the substrate is selected from a group consisting of a belt, a substrate attached to the belt, a drum, a substrate attached to the drum, and a combination thereof. (Item 115) The method or apparatus of item 114, wherein the substrate is a substantially columnar drum having an outer diameter of at least about 50 centimeters. (Item 116) The method or apparatus of item 1, wherein the preliminary main assembly or a nanofiber assembly in which the main assembly is patterned. (Item 117) Item 116. The method or apparatus according to item 116, wherein the patterned nanofiber assembly is used to determine the diameter of the twisted yarn. (Item 118) Item 116. The method or apparatus of item 116, wherein the patterned nanofiber assembly comprises at least one of carbon nanofiber forests. (Item 119) The patterned assembly comprises a nanofiber forest, and the patterned nanofiber assembly is a deposition of a patterned catalyst on a substrate used for nanofiber forest growth, a nanofiber forest. The method or apparatus of item 116 provided by cutting a pattern into, and by a method selected from a group consisting of combinations thereof. (Item 120) The patterned assembly of nanofibers is such that adjacent strips of nanofiber forest are parallel and virtually free of nanofibers, different types of nanofibers, different heights of nanofibers, presence of coatings or Item 116, an assembly separated by features selected from a group consisting of nanofibers that differ in either of the coating types, nanofibers that have been chemically treated, and combinations thereof. Method or device. (Item 121) The patterned assembly of nanofibers is on a moving substrate, and the patterning of the patterned assembly provides parallel nanofiber strips that are oriented along the direction of movement of the substrate, item 116. Method or device. (Item 122) Item 121. The method or apparatus of item 121, wherein the parallel nanofiber strips are at least partially patterned along the length of the parallel nanofiber strips. (Item 123) The method or apparatus of item 121, wherein the parallel nanofiber strips are used to separately produce the twisted yarn, which is a single twisted yarn. (Item 124) The plying contains nanofibers having characteristics selected from a group consisting of different lengths, different chemical compositions, different coatings, and combinations thereof, and the plying is a main assembly, a preliminary main assembly, and theirs. The method of item 1 or the device of item 2 or 3 which is drawn and twisted from the same assembly selected from a group of combinations. (Item 125) The method or apparatus of item 124, wherein the assembly comprises at least one nanofiber forest. (Item 126) Item 125. The method or apparatus of item 125, wherein the nanofibers having different characteristics are drawn from different regions of the assembly, and the different characteristics are selected from a group consisting of different types, different surface treatments, and combinations thereof. (Item 127) The main assembly (a) To make a sheet containing the nanofibers, which are mainly oriented in one direction, and (b) Pulling out the nanofibers from the sheet The method of item 1 or the device of item 2 or 3 obtained by. (Item 128) The nanofibers in the main assembly are oriented primarily in one direction by applying an alignment field to a fluid nanofiber dispersion, which consists of a magnetic field, an electric field, a shear flow field, and a combination thereof. Item 1 method or item 2 or 3 device selected from the group. (Item 129) The method or apparatus of item 128, wherein the fluid is substantially removed after the orientation. (Item 130) Item 1 method or item 2 in which the yarn strengthening agent is applied and the yarn strengthening agent has the effect of increasing the electrical conductivity of the twisted yarn higher than the electrical conductivity of the twisted yarn to which the yarn strengthening agent is not applied. Or 3 devices. (Item 131) The electrical conductivity of the twisted yarn is increased by incorporating an electrically conductive material into the twisted yarn, and the electrically conductive material is selected from a group consisting of conductive polymers, metals, alloys, and combinations thereof, item 1. Method or device of item 2 or 3. (Item 132) Item 131. The method or apparatus of item 131, wherein the electrically conductive material comprises a conductive polymer, wherein the conductive polymer comprises a dopingable organic polymer that is electrochemically polymerized with a twisted yarn. (Item 133) The method of item 1 or the apparatus of item 2 or 3, further comprising a post-production chemical reaction of the produced twisted yarn. (Item 134) The method of item 1 or the device of item 2 or 3, further comprising incorporating the twisted yarn into the fabric. (Item 135) The method or apparatus of item 134, wherein the incorporation of the twisted yarn into a woven fabric comprises a weaving method. (Item 136) (a) The twisted yarn has an outer surface and an inner surface. (b) The post-production chemical reaction occurs primarily on the outer surface of the twisted yarn and (c) The method or apparatus of item 133, wherein the nanofibers inside the twisted yarn are primarily electrically conductive nanofibers. (Item 137) The method or apparatus of item 133, wherein the post-production chemical reaction comprises a reaction facilitated by irradiation selected from the group consisting of electron beam, ion beam, microwave, radio frequency, and combinations thereof. (Item 138) The method or apparatus of item 137, wherein the irradiation is carried out in the presence of a chemical agent that promotes the post-production chemical reaction. (Item 139) The method or apparatus of item 134, wherein the nanofibers in the twisted yarn are primarily carbon nanotubes on a weight basis. (Item 140) The method or apparatus of item 134, wherein the nanofibers are primarily multilayer carbon nanotubes on a weight basis. (Item 141) The method or apparatus of item 140, wherein the multi-walled carbon nanotubes primarily have a diameter of up to about 100 nm. (Item 142) The method of item 1 or the apparatus of item 2 or 3, wherein the nanofibers include hollow nanofibers. (Item 143) The method or apparatus of item 142, wherein the hollow nanofibers are at least partially filled with a drug. (Item 144) The main assembly (a) Absorbing liquids containing volatile components, and (b) Then evaporate the volatile components in the liquid Item 1 method or item 2 or 3 device densified by. (Item 145) (a) The main assembly is an oriented nanofiber ribbon obtained by cutting or otherwise forming a nanofiber sheet into a ribbon shape. (b) The nanofibers are predominantly aligned in one direction in the plane of the sheet and (c) The method of item 1 or the device of item 2 or 3, wherein the ribbon length is along the direction of alignment. (Item 146) (a) The main assembly is an oriented nanofiber ribbon, and (b) The method or apparatus of item 145, wherein the product of the ribbon thickness and ribbon width of the nanofiber ribbon is up to about 1% of the square of the average nanofiber length relative to at least about 20% by weight of the nanofibers in the strands. (Item 147) 146. The method or apparatus of item 146, wherein the product is up to about 0.5% of the square of the average nanofiber length relative to at least about 50% by weight of the nanofibers in the twisted yarn. (Item 148) (a) The preliminary main assembly includes a nanofiber ribbon in which the nanofibers are oriented primarily in the plane of the ribbon and orthogonal to the direction of the ribbon, and (b) The nanofibers are drawn from the ends of the nanofiber ribbon to form the main assembly either before or between the plyings. Item 1 method or item 2 or 3 device. (Item 149) (a) The preliminary main assembly comprises a nanofiber sheet or ribbon in which the nanofibers are oriented primarily perpendicular to the nanofiber sheet, and (b) The nanofibers are drawn from the sides of the nanofiber sheet or ribbon to form a twisted main assembly. Item 1 method or item 2 or 3 device. (Item 150) (A) The steps of arranging the nanofibers so as to provide a substantially parallel nanofiber arrangement with some degree of interfiber connectivity within the nanofiber arrangement, and (b) substantially twisting the ribbon or sheet. A method of producing a nanofiber ribbon or sheet, comprising the step of pulling the nanofibers out of a nanofiber array, without, as a ribbon or sheet having a width of at least about 1 mm. (Item 151) A device for manufacturing nanofiber ribbons or sheets. (a) The step of arranging the nanofibers so as to provide a substantially parallel nanofiber array having some degree of interfiber binding within the nanofiber array. (b) A device capable of performing a method comprising pulling the nanofibers out of a nanofiber array as a ribbon or sheet having a width of at least about 1 mm without substantially twisting the ribbon or sheet. (Item 152) (a) Substantially parallel nanofiber arrays with some degree of interfiber connectivity within the nanofiber array, and (b) Nano, including a pull-out mechanism that is an operable pull-out mechanism that pulls nanofibers out of a nanofiber array as a ribbon or sheet that is at least about 1 mm wide without substantially twisting the ribbon or sheet. A device for manufacturing fiber ribbons or sheets. (Item 153) The method of item 150 or the device of item 151 or 152, further comprising depositing the ribbon or sheet on a substrate. (Item 154) (a) The important components of the nanofibers have a maximum thickness of less than about 500 nm and (b) The nanofibers have a minimum length-to-thickness ratio of at least about 100, and (c) The method of item 150 or the device of item 151 or 152, where the minimum ratio of nanofiber length to ribbon or sheet thickness is greater than about 5. (Item 155) The method of item 150 or the device of item 151 or 152, wherein the ribbon or sheet has a continuous length of at least about 1 meter. (Item 156) The method of item 150 or the device of item 151 or 152, wherein the ribbon or sheet is at least about 4 cm wide. (Item 157) 153. The method or apparatus of item 153, wherein the deposition of the ribbon or sheet onto the substrate comprises wrapping. (Item 158) 153. The method or apparatus, wherein the substrate comprises a spindle. (Item 159) The method of item 150 or the device of item 151 or 152, wherein the nanofiber drawers produce a nanofiber ribbon and the nanofiber ribbons are laminated to form a nanofiber sheet. (Item 160) 159. The method or apparatus of item 159, wherein the stacking comprises a stacking means selected from the group consisting of chemical binders, electron beams, heat treatments, ion beams, radio frequency irradiation, microwave irradiation, and combinations thereof. (Item 161) 159. The method or apparatus, wherein the lamination comprises using an organic polymer. (Item 162) The method of item 150 or the device of item 151 or 152, wherein the nanofiber array is a nanofiber forest. (Item 163) The method or apparatus of item 162, wherein the nanofiber forest comprises carbon nanotubes. (Item 164) 163. The method or apparatus according to item 163, wherein the carbon nanotubes include multi-walled carbon nanotubes. (Item 165) The nanofibers are synthesized on a substrate as a forest of nanotubes in the growth region of the furnace, the substrate is selected from the growth region of the furnace, and the nanofibers in the forest are selected from a group consisting of ribbons, sheets, and combinations thereof. The method or apparatus of item 162, which continuously moves into the area drawn into the form to be. (Item 166) The method of item 150 or the device of item 151 or 152, wherein the nanofiber array is an assembly of patterned nanofibers. (Item 167) The method or equipment of item 166, wherein the nanofiber ribbon is manufactured and the nanofiber patterning assembly is used to determine the width of the nanofiber ribbon. (Item 168) The patterned nanofiber assembly consists of depositing a patterned catalyst on a substrate used for nanofiber forest growth, cutting patterns into an array of nanofibers, and a combination thereof. Item 166 method or device provided by the technology selected from the group. (Item 169) The patterned assembly of nanofibers is such that adjacent strips of nanofiber forest are parallel and virtually free of nanofibers, different types of nanofibers, different heights of nanofibers, presence of coatings or Item 166, item 166, which is an assembly separated by features selected from a group consisting of nanofibers of different coating types, nanofibers of different chemical treatments, and combinations thereof. Method or device. (Item 170) A single nanofiber yarn containing at least about 10,000 nanofibers in a 1 square micron cross-sectional area of the single nanofiber yarn. (a) The nanofiber single yarn is at least about 1 meter long. (b) The nanofiber single yarn has a diameter less than about 10 microns, and (c) The nanofiber single yarn is a form selected from a group consisting of unsuperposed, superposed, and combinations thereof. Nanofiber single yarn. (Item 171) Item 170 nanofiber single yarn, where at least about 100,000 nanofibers pass through the 1 square micron cross-sectional area of the nanofiber single yarn. (Item 172) Item 170 nanofiber single yarn with a diameter of up to about 5 microns. (Item 173) Item 170 nanofiber single yarn with a diameter of up to about 2 microns. (Item 174) Item 170, the nanofiber single yarn, wherein the nanofiber single yarn is electrically conductive. (Item 175) Item 171 nanofiber single yarn, wherein the nanofiber single yarn has a toughness of at least about 10 J / g. (Item 176) Item 175 Nanofiber single yarn, wherein the nanofiber single yarn is a single twisted yarn of nanofiber. (Item 177) Item 170 nanofiber single yarn, wherein the nanofiber single yarn contains substantially no polymer. (Item 178) The nanofiber single yarn of item 170, wherein the nanofiber single yarn has or does not have a periodic series of knots. (Item 179) Item 170 nanofiber single yarn, wherein the nanofiber single yarn is periodically patterned along the length. (Item 180) The nanofiber single yarn is at least due to periodic changes in properties selected from the group consisting of the twist of the nanofiber, the diameter of the yarn, the composition of the nanofiber, and the structure of the yarn, the material overcoated with the nanofiber, and combinations thereof. Item 179 nanofiber single yarn, partially periodically patterned. (Item 181) 179. The nanofiber single yarn of item 179, wherein the nanofiber single yarn is periodically patterned along the length direction of the yarn to give a periodic change in electrical conductivity to different yarn compartments. (Item 182) The nanofiber single yarn is periodically patterned along the length direction of the yarn to result in a periodic change in the porosity of the yarn that can be used to achieve a periodic change in the absorbency of the yarn. Item 179 nanofiber single yarn. (Item 183) Item 170 nanofiber single yarn, wherein the nanofiber single yarn is substantially twisted along the entire length of the nanofiber single yarn. (Item 184) Item 170 nanofiber single yarn, wherein the nanofiber single yarn is substantially untwisted and infiltrated with an agent that results in a bond between the fibers. (Item 185) Item 184 nanofiber single yarn, wherein the agent comprises an organic polymer. (Item 186) Item 135, the nanofiber single yarn, wherein the tensile strength of the nanofiber single yarn is reduced by an average of up to about 20% as a result of one knot in the nanofiber single yarn. (Item 187) Twisted yarn manufactured by the method of item 1. (Item 188) Protective garment containing item 175 nanofiber single yarn. (Item 189) Protectiveness as a result of properties selected from the group consisting of low permeability to bacteria, high radio wave absorption, high microwave absorption, high thermal conductivity, high electrostatic discharge capability, high performance to prevent mechanical intrusion, and combinations thereof. Protective woven fabric containing nanofiber single yarn of item 175. (Item 190) Protective fabric of item 189, in which nanofiber single yarns are densely woven into the fabric to provide a high degree of resistance to air flow. (Item 191) Protective fabric of item 190, wherein the resistance to airflow is similar to the resistance to airflow of the canvas fabric. (Item 192) A woven fabric in which the electrically conductive nanofiber single yarn of item 174 is incorporated into the woven fabric as a part of an acoustic array containing antennas, sensors, and ferroelectric elements. (Item 193) A fabric comprising a nanofiber single yarn of item 170 that is at least partially incorporated to form an interconnect between the opposing surfaces of the fabric by applying pressure to bring the opposing surfaces into contact. (Item 194) The fabric of item 193, wherein the nanofiber single yarn is in a loop shape that interacts with the elements of the opposing surface that act as hooks that hold the opposing surfaces in contact with each other. (Item 195) The fabric of item 194, wherein the loops and hooks are characterized by good electrical conductivity, good thermal conductivity, and properties selected from the group consisting of combinations thereof. (Item 196) Item 192 woven fabric in which electrically conductive nanofiber single yarn is incorporated into the woven fabric as a sensor selected from the group consisting of chemical and mechanical sensors. (Item 197) The sensor is a chemical sensor, and the response of the chemical sensor is a change in characteristics selected from the group consisting of the electrical conductivity, thermopower, electrochemical capacitance, and a combination thereof. Item 196 textiles brought about by. (Item 198) (a) Electrically conductive nanofiber single yarns are incorporated into the fabric as parts of an acoustic array containing ferroelectric elements. (b) The ferroelectric element at least partially coats an electrically conductive nanofiber single yarn, separates adjacent electrically conductive yarns and fibers, and (c) At least partially electrically polling at least approximately at right angles to the direction of the single yarn, or, if the single yarns, the direction of the overlapped yarn, at least a portion of the ferroelectric element. The fabric of item 192 to be processed. (Item 199) The fabric of item 198, wherein the direction of polling is at least approximately orthogonal to the local plane of the fabric. (Item 200) A woven fabric that incorporates at least two electrically conductive wires, each of which contains the nanofiber single yarn of item 174. (Item 201) (a) At least a significant portion of electrically conductive nanofiber monofilaments do not have an insulating surface coating. (b) The woven fabric further comprises an electrically insulating yarn having a diameter at least 5 times that of the electrically conductive nanofiber single yarn. (c) The woven fabric of item 200, wherein the insulating yarn prevents contact between electrically conductive nanofiber single yarns. (Item 202) A device containing a single-walled nanotube fiber of item 170, selected from the group consisting of electronic switches, electrical transformers, electromagnets, and combinations thereof. (Item 203) A woven fabric containing a single-walled nanotube fiber of item 170 and containing a device selected from the group consisting of electronic switches, electrical transformers, electromagnets, and combinations thereof. (Item 204) A composite material comprising a nanofiber single yarn of item 170 that forms a composite fiber in combination with a material selected from the group consisting of polymers, metals, and combinations thereof. (Item 205) A fabric containing the nanofiber single yarn of item 170, in which the nanofiber single yarn is incorporated into the fabric. (Item 206) Nanofiber single yarns are configured for use in products, said products are electrochemical devices, scaffolds for tissue growth, electric heaters, incandescent lamp sources in the visible and infrared light regions, electron electric field emission sources, A product containing nanofiber single yarn of item 170, selected from the group consisting of electron heat emitting sources, electronic textile components, thermochromic elements, fuel cells, and combinations thereof. (Item 207) The product of item 206, wherein the nanofiber single yarn contains carbon nanotubes. (Item 208) A tissue growth scaffold containing the nanofiber single yarn of item 170, wherein the nanofiber single yarn is used as a tissue growth scaffold. (Item 209) Item 208. The scaffold of item 208, wherein the scaffold results in the proliferation of functional neurons. (Item 210) The scaffold of item 208, wherein the scaffold connects to a neuron. (Item 211) The nanofiber monofilament initially has a high degree of rigidity as a result of the uptake of the drug contained within the nanofiber monofilament and is at least partially removed during the biological processes that occur during tissue growth. , Item 208 scaffolding. (Item 212) A thermochromic material system comprising the nanofiber single yarn of item 170, wherein the nanofiber single yarn is used in the thermochromic material system. (Item 213) The thermochromic material system of item 212, wherein the thermochromic material comprises a material selected from the group consisting of thermochromic liquid crystals, thermochromic polymers, and combinations thereof. (Item 214) An electrochemical device containing a nanofiber single yarn of item 170, the electrochemical device undergoes switchable changes in properties selected from the group consisting of transparency, absorbency, reflectivity, and combinations thereof. To provide, electrochemical device. (Item 215) The electrochemical device of item 214, wherein the switchable changes in properties include changes in wavelength. (Item 216) The electrochemical device of item 214, wherein the switchable changes in properties are at least partially due to electrochemically induced changes within the nanofiber single yarn. (Item 217) Item 170 nano, where the field emission source is a part of a device selected from the group consisting of flat panel displays, lamps, gas discharge tubes that provide surge protection, x-ray generators, microwave generators, and combinations thereof. A field emission source containing a single fiber yarn. (Item 218) A field emission source of item 217, further comprising a phosphor to provide light emission. (Item 219) The field emission source is the field emission source of item 217, which uses electron emission from the tip of a nanofiber single yarn with a diameter of up to about 10 microns. (Item 220) The field emission source device comprising the nanofiber single yarn of item 170, wherein the nanofiber single yarn is axially configured in the field emission source device, and the electric field emission source device has a columnar shape. (Item 221) A field emission device incorporating the twisted yarn of item 1 in which the twisted yarn contains carbon nanotubes. (Item 222) The nanofiber single yarn is incorporated into a field emission source, where the field emission originates primarily from the sides of the nanofiber single yarn, the field emission source comprising the nanofiber single yarn of item 170. (Item 223) A field emission source of item 217, said field emission source, comprising processing the nanofiber monofilament to supply nanotube fibers extending from the surface of the nanofiber monofilament to provide enhanced field emission. A field emission source manufactured by the method. (Item 224) The field emission source of item 223, wherein the treatment is a method selected from the group consisting of plasma treatment, mechanical wear, sonication, thermal annealing, chemical treatment in an oxidizing environment, and combinations thereof. Field emission sources including. (Item 225) A transparent conductor produced by the method of item 150 comprising electrically conductive nanofibers, which is applied as an electrode on a substrate. (Item 226) A device containing the transparent conductor of item 225, (a) The device is selected from a group consisting of liquid crystal displays, light emitting displays, solar cells, switchable transparent windows, lasers, light modulators, field emission devices, electronic switches, optical polarizers, and combinations thereof. And then (b) A device, wherein the transparent conductor is a transparent conductor that functions as a component selected from the group consisting of electrodes, polarizing optical elements, and combinations thereof. (Item 227) An electrochemical device containing the nanofiber single yarn of item 170. (a) The electrochemical device includes a battery, a supercondenser, an electromechanical actuator for converting electrical energy into mechanical energy, an electromechanical actuator for converting mechanical energy into electrical energy, and a fuel cell. , And a group of combinations thereof (b) The device utilizes a nanofiber single yarn as the device electrode and (c) An electrochemical device in which the electrolyte is present in the electrodes of a single nanofiber yarn and provides an ionic conductive path to the counter electrode. (Item 228) Nanofiber single yarn is an electrochemical device of item 227, which comprises a single twisted yarn of carbon nanofibers filled with an electrolyte. (Item 229) An electrochemical device of item 228, further comprising a second device electrode comprising another electrolyte-filled carbon nanotube twisted yarn, wherein both electrolyte-filled carbon nanotube twisted yarns are superposed together. (Item 230) Electrically conductive wire containing the nanofiber single yarn of item 174. (Item 231) The electrically conductive wire of item 230, which is superconducting at any temperature. (Item 232) Item 231 of the electrically conductive wire, wherein the electrically conductive wire is MgB.₂, Nb₃Sn, or MoS_9-xI_xAn electrically conductive wire containing nanofibers of material selected from the group consisting of, where X is between about 4.5 and about 6. (Item 233) Item 231 Electrically conductive wire, which is insulated on the yarn surface and contains electrically conductive nanofiber single yarn, the insulation of the yarn surface is the chemical conversion of the nanofibers on the yarn surface, the coating of insulating polymer, Conductive wire due to conditions selected from the group consisting of a sheath of insulating nanofibers twisted onto the thread surface, and the presence of combinations thereof. (Item 234) Item 231. An electrically conductive wire comprising nanoparticles in an electrically conductive nanofiber single yarn, wherein the nanoparticles are selected from the group consisting of Pt and its alloys. (Item 235) The electrically conductive wire of item 231 which contains an electrolyte in the electrically conductive nanofiber single yarn. (Item 236) A fuel cell comprising the electrically conductive nanofiber yarn of item 174, wherein the electrically conductive nanofiber yarn forms an electrode of the fuel cell, and the electrically conductive nanofiber single yarn contains a catalyst and an electrolyte. battery. (Item 237) A microfluidic circuit device utilizing the nanofiber single yarn of item 170. (Item 238) Item 237 microfluidic circuit device, which is a three-dimensional structure. (Item 239) Item 237 microfluidic circuit device using knots to transport fluid between different nanofiber single yarns. (Item 240) The microfluidic circuit device of item 237, wherein the nanofiber single yarn is a single twisted yarn of nanofiber. (Item 241) Woven fabric containing the microfluidic circuit device of item 237. (Item 242) Nanofiber products manufactured by the method of item 150. (Item 243) Item 170 nanofiber single yarn that is further superposed to produce a superposed twisted yarn. (Item 244) Item 174 nanofiber single yarn, said nanofiber single yarn absorbing material and selected from the group consisting of electrical, microwave, radio frequency, visible light, infrared light, and combinations thereof. Nanofiber single yarns that at least partially release the material as a result of at least partial heating of the electrically conductive yarn by using radiation absorption. (Item 245) A self-healing structure of microfluidics, including nanofiber monofilaments according to item 170, which provides mechanical reinforcement and enhances microfluidic and self-healing functions. (Item 246) An incandescent electric light source containing the nanofiber single yarn of item 170, wherein the nanofiber single yarn is twisted, and the nanofiber single yarn contains an incandescent element of an incandescent electric light source. (Item 247) Item 246 incandescent electric light source in which nanofiber single yarns are superposed. (Item 248) An incandescent electric light source, including a twisted yarn manufactured by the method of item 1, wherein the twisted yarn is electrically conductive and contains an incandescent element of an incandescent electric light source. (Item 249) A product containing twisted yarn manufactured by the method of item 1 and (a) The product is selected from the group consisting of electrochemical devices, tissue growth scaffolds, electric heaters, incandescent light sources, field emission sources, electron thermal radiation sources, thermochromic elements, fuel cells, and combinations thereof. (b) Twisted yarn is a product that is electrically conductive. (Item 250) A method of polling a fabric according to item 199 by applying an electric field that is at least approximately perpendicular to the local plane of the fabric. (Item 251) A method of incorporating an electronic chip into a yarn assembly containing a single nanofiber yarn of item 170. (a) Steps to disperse free electronic chips in a fluid medium, (b) Steps to structure the yarn assembly containing the nanofiber single yarn to provide a docking site for the electronic chip, (c) A method comprising the step of flowing a fluid medium containing the electronic chip over the thread assembly so that the electronic chip is selectively self-assembled in the docking site. (Item 252) A method of patterning the nanofiber single yarn of item 170 along the length of the nanofiber single yarn, which is photopolymerization; polymer reaction induced by an electron beam; mass transfer induced by pressure; material deposition, A method comprising a patterning technique selected from a group consisting of liquid treatment, gas phase treatment, and plasma treatment for removal, deformation; and combinations thereof. (Item 253) A method of patterning a nanofiber single yarn of item 170 along the length of the nanofiber single yarn, the method comprising the use of periodic patterning of the nanofiber array from which the nanofiber single yarn is produced. (Item 254) The method of item 253, wherein the periodic patterning is at least partially provided by the periodic patterning of the nanofiber forest arrangement from which the nanofiber single yarn is drawn. (Item 255) (a) Steps to select porous yarns containing nanofibers, (b) The step of knotting the thread to form a star thread, (c) Gas; vapor; plasma; liquid; solution; fluid dispersion; supercritical liquid; material selected from the group consisting of melts; and electrochemical deposition, electrochemical material removal; electrochemical polymerization; and Conditions that result in these combinations; methods involving the step of achieving region-selective material treatment of the thread by exposing the star thread to. (Item 256) The method of item 255, further including the use of star thread in the lithographic method. (Item 257) The method of item 256, wherein the lithograph method is used to make a circuit selected from a group consisting of electrical circuits, fluid circuits, thermal circuits, and combinations and elements thereof. (Item 258) The method of item 255, wherein at least one of the knotting and exposure steps changes the yarn density, the density change predominantly causing the region-selective material treatment. (Item 259) The method of item 255, wherein the thread comprises nanofibers. (Item 260) (a) As a result of knotting, selective absorption of the protective agent occurs in different regions of the star thread with different densities, and (b) The method of item 258, wherein the material treatment is selectively performed on the yarn region where there is little or less protective agent. (Item 261) (a) Steps to select a substrate from a group consisting of elastically deformable substrates, electrically deformable substrates, and combinations thereof. (b) A step of elongating a substrate to form a deformed substrate, wherein the elongation is a step selected from a group consisting of elastic elongation, electrical elongation, and combinations thereof. Deformable, including (c) a step of adhesively applying a nanofiber sheet or ribbon to the deformed substrate, and (d) a step of allowing at least a partial return of the elongation after the adhesive application step. A method of manufacturing nanofiber sheets or ribbons. (Item 262) 261. The method of item 261, wherein the substrate is a substrate sheet or ribbon having opposite surfaces and the nanofiber sheet or ribbon is adhesively applied to the opposite surface of the substrate when the substrate is in the stretched state. (Item 263) 261. The method of item 261 in which the nanofiber sheet or ribbon comprises carbon nanotubes. (Item 264) 263. The method of item 263, wherein the nanofiber sheet or ribbon comprises predominantly carbon nanotubes and the nanofiber sheet or ribbon is first formed in the form of a sheet or ribbon by a withdrawal method that occurs primarily in the solid state. (Item 265) 264. The method of item 264, wherein the sheet or ribbon is pulled out of the nanotube forest. (Item 266) A method of embedding an elastically deformable nanofiber sheet between two elastomer polymer sheets: (a) Steps to select the first elastomeric polymer sheet, (b) A step of elastically stretching the first elastomer polymer sheet to form a deformed substrate. (c) Steps of adhesively applying the nanofiber sheet to the deformed substrate, (d) A step that allows the elastic elongation to return, at least in part, after the adhesive application step. (e) When the first elastomer polymer sheet is in a relaxed or partially relaxed state, the step of applying the resin precursor for the second elastomer polymer sheet to the nanofiber sheet, and (f) A method comprising the step of curing a resin precursor to form a second elastomeric polymer sheet while the first elastomeric polymer sheet is in a relaxed or partially relaxed state. (Item 267) The method of item 266, wherein the nanofiber sheet contains carbon nanotubes. (Item 268) 261. The method of item 261 in which the substrate is a material that can be used as an electromechanical actuator and the nanofiber sheet or ribbon is electron conductive. (Item 269) A product manufactured by the method of claim 261 in which a nanofiber sheet is adhered to a deformed substrate. (Item 270) The product of item 269, wherein the substrate comprises an elastically deformable substrate selected from the group consisting of rubber and elastomeric fabrics. (Item 271) Item 269 product, the substrate containing an electrostrictive rubber substrate. (Item 272) The product of item 271, wherein the substrate is a sheet containing silicone rubber. (Item 273) A product of item 270, wherein the substrate comprises an elastomeric fabric containing an elastomeric polymer. (Item 274) Item 270 products further containing fibers selected from the group consisting of cotton, polyester, and combinations thereof. (Item 275) The product of item 268, wherein the nanofiber sheet is electron conductive and the substrate is elastically deformable and substantially electronically insulating. (Item 276) A device comprising at least two deformable nanofiber sheets or ribbons of item 268, wherein the device is (i) electromechanical actuation, (ii) conversion of mechanical energy to electrical energy, ( Iii) can be actuated for the damping of mechanical vibrations, and (iv) the function selected from the group consisting of combinations thereof. (b) At least two deformable nanofiber sheets or ribbons are elastically deformable and electron-conducting nanofiber sheets or ribbons, respectively. (c) A device in which at least two deformable nanofiber sheets or ribbons act as electrodes on the device. (Item 277) Item 276 device, wherein the device is operable for electromechanical operation and further comprises an electrostrictive rubber, or a conductive organic polymer capable of electrochemical doping. (Item 278) The device of item 276, further comprising electrostrainable or piezoelectric rubber, in which the device is operational for the conversion of mechanical energy to electrical energy and is capable of undergoing at least about 25% reversible elastic deformation. (Item 279) A device of item 276, wherein the device is operable for mechanical damping and further comprises an electrostrictive or piezoelectric rubber capable of undergoing reversible elastic deformation of at least about 25%, wherein the mechanical damping is A device obtained by controlling the transport of electric current between the electrodes. (Item 280) It is a method of spinning yarn containing nanofibers. (a) The step of pulling out the main assembly containing the aligned nanofibers from the nanofiber forest, the angle between the pulling direction and the alignment direction of the nanofibers in the forest is between about 90 ° and about 5 °. Steps and (b) A method comprising the steps of producing nanofiber plying by twisting the main assembly of nanofibers around a shaft that is approximately aligned with the nanofibers of the main assembly. (Item 281) Item 280 method in which the nanofiber forest is on the substrate. (Item 282) The method of item 281 where the nanofiber forest is not supported by the substrate used for the growth of the nanofiber forest. (Item 283) The method of item 280, wherein the angle is between 90 ° and 50 °. (Item 284) Item 280. The method of item 280, wherein the nanofibers from the nanofiber forest were continuously linked during the withdrawal steps, maintained or remained connected during the withdrawal steps, or a combination thereof. (Item 285) Item 280 method, in which the nanofibers drawn during the pull-out step form a nearly planar wedge between the nanofiber forest and the nanofiber focusing zone. (Item 286) The method of item 285, wherein the wedge becomes a thread up to about 5 mm from the nanofiber forest. (Item 287) The method of item 280, wherein the nanofibers from the nanofiber forest have a minimum length-to-thickness ratio of at least about 10 in the thinnest lateral direction. (Item 288) The method of item 280, wherein the nanofibers from the nanofiber forest have a minimum ratio of length to thickness of at least about 100 in the thinnest lateral direction. (Item 289) The method of item 280, wherein the nanofibers from the nanofiber forest have a minimum ratio of length to thickness of at least about 1000 in the thinnest lateral direction. (Item 290) Item 280 method, where the withdrawal step and the plying step are each performed at a maximum of about 100 ° C. (Item 291) Item 290 method in which heat is applied to the nanofibers or substrate during at least one of the withdrawal and plying steps. (Item 292) 280. The method of item 280, wherein the nanofibers in the nanofiber forest contain carbon nanotubes. (Item 293) 292. The method of item 292, wherein the carbon nanotubes are multi-walled carbon nanotubes. (Item 294) Item 280 method, further comprising the step of treating the nanofiber forest with a thread strengthening agent. (Item 295) The nanofibers are synthesized on the substrate as a nanofiber forest in the growth region of the furnace, and the substrate is in the second region where the nanofibers in the nanofiber forest are drawn out during the withdrawal step from the growth region of the furnace. Item 280 way to move continuously to. (Item 296) 295. The method of item 295, wherein the substrate is selected from a group consisting of belts, drums, substrates attached to drums, and combinations thereof. (Item 297) Item 280 method, in which the main assembly contains nanotube ribbons or sheets. (Item 298) It is a method of spinning yarn containing nanofibers. (a) The step of drawing from the nanofiber array as synthesized to form a major assembly containing multiple nearly aligned nanofibers, where the nanofibers from the nanofiber array are drawn during the drawing step. With steps that are continuously connected, maintain the connection of previous withdrawal steps between withdrawal steps, or a combination thereof, (b) The step of twisting the main assembly of aligned nanofibers around an axis that is almost aligned with the nanofibers to produce a nanofiber plying, where the length of the main nanofibers is the circumference of the nanofiber twisted yarn. A method that includes steps that are at least 5 times that of. (Item 299) The drawer is from a nanofiber array, which can be up to about 0.05 g / cm.³Dense with a degree, method of item 298. (Item 300) 298. The method of item 298, wherein the nanofiber arrangement comprises approximately unaligned nanofiber arrangements or under-aligned nanofiber arrangements. (Item 301) The method of item 298, where the nanofiber array is a highly aligned nanofiber forest. (Item 302) The method of item 300, where the main assembly is a nanofiber ribbon or sheet containing highly aligned nanofibers. (Item 303) (a) The step of collecting the main assembly as a parallel oriented stack of ribbons or sheets on the substrate, or ribbons or sheets on the substrate. (b) Then the step of removing the ribbon or sheet or the oriented stack of the ribbon or sheet from the substrate, and (c) the configuration of the ribbon or sheet (or stack thereof) around the nanotube alignment direction. The method of item 302, further comprising the steps of twisting the elements to produce a twisted yarn. (Item 304) 298. The method of item 298, wherein the nanofibers primarily contain carbon nanotubes. (Item 305) A method of producing twisted yarn containing nanofibers. (a) Using a liquid-based method, with the step of spinning nanofiber yarns containing at least 20% by weight nanofibers, (b) A method including a step of twisting around the yarn direction to produce a twisted yarn. (Item 306) The method of item 305, wherein the minimum ratio of nanofiber length to thread circumference is at least about 5. (Item 307) The method of item 305, wherein the main assembly is indirectly or directly formed into the yarn by cohesive spinning of nanofibers. (Item 308) 307. The method of item 307, wherein the cohesive spinning directly or indirectly provides a composite comprising polymers and nanofibers. (Item 309) Cohesive Spinning A method of item 308, further comprising a withdrawal process that results in permanent elongation of the nanofiber yarn, wherein the plying is performed before, during, or after the withdrawal process. (Item 310) The method of item 309, wherein the plying is primarily carried out while the polymer is in a fluid or semi-fluid state. (Item 311) The method of item 309, wherein the polymer is substantially removed after the polymer-containing nanofiber yarn has been drawn out but before substantial plying has been introduced. (Item 312) The method of item 311 in which substantial polymer removal is by thermal decomposition. (Item 313) Coagulation-based spinning involves spinning from a solution in which carbon nanotubes are dispersed in a spinning solution, the spinning solution being selected from the group consisting of acids, superacids, organic liquids, water and combinations thereof, item 307. the method of. (Item 314) 313. The method of item 313, wherein at least one of the spinning solution and the coagulating solution comprises polyvinyl alcohol. (Item 315) The method of item 305, wherein the nanofibers contain carbon nanotubes. (Item 316) 315. The method of item 315, wherein the nanofibers primarily contain carbon nanotubes. (Item 317) 316. The method of item 316, wherein the nanotubes primarily contain single-walled carbon nanotubes. (Item 318) A method of manufacturing nanofiber ribbons or sheets from nanofiber forests. (a) A step in the production of nanofiber forests containing nanofibers, where nanofiber forests are suitable for pulling ribbons or sheets at least about 1 mm wide from the nanofiber forests. A step with a side wall and (b) a step of connecting the attachment to the side wall or near the side wall of the nanofiber forest. (c) A method comprising pulling a nanofiber ribbon or sheet out of the nanofiber forest by pulling the attachment. (Item 319) The method of item 318, where the nanofiber forest is a carbon nanotube forest containing carbon nanotubes. (Item 320) Carbon nanotubes are multi-walled carbon nanotubes with a diameter of about 10 nm, and the forest density at the base of the carbon nanotube forest is at least about 20 billion nanotubes / cm.²The method of item 319. (Item 321) The method of item 319, wherein the percentage of the base area occupied by the nanotubes in the carbon nanotube forest is at least about 4%. (Item 322) The method of item 319, where the percentage of base area occupied by nanotubes in the carbon nanotube forest is up to about 40%. (Item 323) When measured at the base of the carbon nanotube forest, the product of the number of nanotubes per unit area in the carbon nanotube forest and the diameter of the carbon nanotubes is in the range between about 0.16 and about 1.6, item 319. Method. (Item 324) The method of item 319, in which carbon nanotubes in a carbon nanotube forest are intermittently bundled. (Item 325) The method of item 319, wherein at least 20% of the carbon nanotubes initiated in the base region of the carbon nanotube forest essentially extend to the top of the carbon nanotube forest. (Item 326) The method of item 319, where the height of the carbon nanotube forest is at least about 50 microns. (Item 327) The method of item 319, where the height of the carbon nanotube forest is at least about 100 microns. (Item 328) The method of item 318, where the nanofibers are pulled simultaneously from essentially the total height of the side walls of the nanofiber forest. (Item 329) The withdrawal step is performed at a speed of at least 5 meters per minute, item 319 method. (Item 330) A nanofiber ribbon or sheet manufactured by the method of item 319, which is transparent and electrically conductive. (Item 331) A nanofiber ribbon or sheet manufactured by the method of item 319, which is a highly arranged airgel. (Item 332) Item 331 nanofiber ribbon or sheet, 10 μg / cm²Nanofiber ribbons or sheets with less area density. (Item 333) A nanofiber sheet manufactured by the method of item 319, having a width of at least about 5 cm. (Item 334) Nanofiber ribbon or sheet manufactured by the method of item 331, up to approximately 0.005 g / cm³Nanofiber ribbon or sheet with a density of. (Item 335) The nanofiber ribbon or sheet of item 331, which is attached to the substrate. (Item 336) The nanofiber ribbon or sheet of item 335, wherein the substrate comprises a material selected from the group consisting of plastics, adhesive tapes, glass, metals, papers, and combinations thereof. (Item 337) A layered layer comprising a nanofiber ribbon or sheet manufactured by the method of item 319, wherein the nanofiber ribbon and the sheet are oriented with each other but do not have the same preferred alignment direction of the carbon nanotubes. (Item 338) (a) A step in producing a carbon nanotube forest containing carbon nanotubes, the carbon nanotube forest is suitable for pulling a ribbon or tube from the carbon nanotube forest, and the ribbon or sheet is at least about 1 mm wide. Yes, the carbon nanotube forest has a step with side walls, (b) The step of connecting the attachment to the side wall of the carbon nanotube forest or near the side wall, and (c) Withdrawing the ribbon or sheet from the carbon nanotube forest by pulling on the attachment, where the ribbon or sheet is a highly oriented airgel ribbon or sheet. (d) The step of infiltrating a sheet or ribbon with a liquid and then evaporating the liquid from the sheet or ribbon, infiltration and evaporation at least partially densifying the sheet or ribbon to form a densified sheet or ribbon. How to include steps and. (Item 339) A densification sheet or ribbon manufactured by the method of item 338, having a maximum thickness of about 100 nm. (Item 340) Area-selective densification is provided for nanofiber ribbons or sheets by distributing the densifying liquid to selected areas, item 339. (Item 341) The method of item 338, wherein the infiltration with a liquid comprises a method selected from the group consisting of vapor condensation, absorption of the liquid, exposure of the liquid to an aerosol, and combinations thereof. (Item 342) 338. The method of item 338, wherein the liquid comprises a substance selected from the group consisting of acetone, ethanol, methanol, isopropyl alcohol, toluene, chloroform, chlorobenzene, liquids having similar aggregation energy densities, and combinations thereof. (Item 343) 338. The method of item 338, wherein the liquid comprises water and a surfactant. (Item 344) 318. The method of item 318, wherein the connecting step comprises using an adhesive means selected from a group consisting of adhesives, pin arrays, or combinations thereof. (Item 345) 344. The method of item 344, wherein the attachment means is at least approximately equivalent to a linear array and the withdrawal direction is at least approximately orthogonal to the direction of the valid linear array. (Item 346) The method of item 345, wherein the attachment connections are near the top and side walls of the forest relative to the nanofiber forest, the connections comprising the use of straight adhesive strips. (Item 347) The method of item 345, where the attachment is connected by a pin array that penetrates between about 1/3 and about 3/4 of the height of the nanofiber forest. (Item 348) The method of item 347, in which different pins in the pin arrangement penetrate into the nanofiber forest at different depths. (Item 349) A method of strengthening threads, ribbons, or sheets containing nanofibers. (a) Infiltration of liquid into thread, ribbon or sheet, and (b) A method comprising evaporating a liquid from a thread, ribbon or sheet to strengthen the thread, ribbon or sheet. (Item 350) 349. The method of item 349, wherein the evaporation step increases the density of threads, ribbons or sheets. (Item 351) The method of item 350, where the increase in density is a factor of at least 100 percent. (Item 352) 349. The method of item 349, wherein the thread, ribbon, or sheet is airgel. (Item 353) The method of item 349, wherein the nanofibers contain carbon nanotubes. (Item 354) 349. The method of item 349, wherein the nanofibers contain carbon nanotubes and the thread, ribbon, or sheet is airgel. (Item 355) 354. The method of item 354, comprising a polymer in which a liquid is dissolved. (Item 356) 353. The method of item 353, wherein the carbon nanotubes are the main component on a weight basis in the yarn, ribbon, or sheet. (Item 357) 353. The method of item 353, wherein the carbon nanotubes are the main components of the yarn, ribbon, or sheet on a volume basis. (Item 358) 357. The method of item 357, wherein the volume of the non-nanofiber component of the thread, ribbon, or sheet is less than one tenth of the volume of the carbon nanotube. (Item 359) 353. The method of item 353, wherein the yarn, ribbon, or sheet is formed by processing carbon nanotube airgel formed in a reactor by chemical vapor deposition. (Item 360) The method of item 353, wherein the thread, ribbon, or sheet is formed from a carbon nanotube forest in a solid state drawer. (Item 361) The polymer is retained on the thread, ribbon, or sheet after evaporation of the liquid used for densification, and the properties of the thread, ribbon, or sheet are during liquid evaporation, after liquid evaporation, or during liquid evaporation and liquid evaporation. The method of item 355, both later, where the thread, ribbon, or sheet is further reinforced by irreversible stretching. (Item 362) The method of item 361, where irreversible elongation is greater than 100%. (Item 363) (a) With the step of infiltrating the liquid and infiltrating the polymer into the thread, ribbon, or sheet after evaporating the liquid from the thread, ribbon, or sheet, and. (b) The method of item 349, further comprising pulling out at least 100% of the polymer infiltrated thread, ribbon, or sheet. (Item 364) After the infiltration and evaporation steps, the yarn, ribbon, or sheet (or at least a portion of the yarn, ribbon, or sheet formed by partitioning along the orientation of the carbon nanotubes) is then twisted and subjected to plying or false twisting. Item 353 method for manufacturing plying. (Item 365) (i) The key components of the nanofibers have a maximum thickness of about 30 nm perpendicular to the nanofiber axis, and (ii) the nanofibers have a length pair of at least about 1000 at the thinnest lateral thickness. It has a minimum thickness ratio, (iii) a minimum ratio of nanofiber length to yarn circumference is at least about 5, and (iv) is introduced in one direction per yarn length for twisted yarn of diameter D. The method of item 353, where the maximum twist is at least about 0.06 / D turns. (Item 366) The method of item 365, where the maximum twist introduced in one direction per yarn length for a twisted yarn of diameter D is at least about 0.12 / D turns. (Item 367) The method of item 349, wherein the liquid infiltration is a method selected from the group consisting of vapor condensation, absorption of liquids, exposure of liquids to aerosols, and combinations thereof. (Item 368) The method of item 353, wherein the liquid used for densification comprises a substance selected from the group consisting of acetone, ethanol, methanol, isopropyl alcohol, toluene, chloroform, chlorobenzene, or liquids having similar aggregation energy densities. (Item 369) The method of item 353, wherein infiltration and evaporation of the liquid occurs while the thread, ribbon, or sheet is attached to the substrate. (Item 370) 369. The method further comprises removing the thread, ribbon, or sheet from the substrate. (Item 371) 353. The method of item 353, wherein the liquid comprises water and a surfactant. (Item 372) 352. The method of item 352, wherein the airgel is formed by the freeze-drying method. (Item 373) The method of item 365, in which the net twist introduced is low enough and the corresponding single yarn helix angle is up to about 5 °. (Item 374) A method of strengthening threads containing nanofibers (a) The step of twisting in the first direction, (b) A step of twisting in the second direction, in which the second direction is opposite to the first direction and the net twist of the twisted yarn in the first and second directions is about zero. And how to include. (Item 375) The method of item 374, wherein the plying is applied in the intermediate position so that the twist in the first direction is introduced on one side of the intermediate position and the twist in the second direction is introduced on the opposite side of the intermediate position. .. (Item 376) The item of twisting the yarn in the first direction is by applying the twisted yarn at the end of the yarn, and twisting the yarn in the second direction by applying the same number of twisted yarns in the opposite direction to the same end of the yarn. 374 methods. (Item 377) (a) The yarn has an increase in tensile strength caused by plying in the first direction. (b) The method of item 374, wherein the yarn retains an increase in tensile strength of at least about 20% after plying in the second direction. (Item 378) (a) The yarn has a first diameter after the plying of the yarn in the first direction. (b) The yarn has a second diameter after the plying of the yarn in the second direction. (c) The method of item 374, wherein the ratio of the first diameter to the second diameter is at least about 0.75. (Item 379) A device that manufactures nanofiber twisted yarn. (a) Nanofiber supply section and (b) A transport tube for transporting nanofibers from supply to collector, (c) A rotatable collector that collects nanofibers from the supply section, (d) A winder that collects nanofiber plyed yarn from the collector while the collector is rotated, and as the twisted nanofiber yarn is recovered from the collector, the nanofibers inside the collector are twisted and the nanofiber twisted yarn. A device that includes a winder to form. (Item 380) The device of item 379, in which the transport tube can be operated to flow gas through the transport tube to carry the nanofibers from the supply to the collector. (Item 381) Equipment of item 379, wherein the nanofiber feeder contains an airgel containing nanofibers. (Item 382) The device of item 381, in which the shape of the airgel is an airgel sheet. (Item 383) The device of item 382, in which the airgel sheet is manufactured by spinning the sheet from a nanofiber forest. (Item 384) Equipment of item 379, further including a duffing tube navel that inserts false twists into the twisted yarn. (Item 385) Equipment of item 379, further including a yarn package around which nanofiber twisted yarn is wound. (Item 386) It is a method of manufacturing nanofiber twisted yarn. (a) Steps to continuously supply nanofibers to the collector, (b) With the step of rotating the collector to form an assembly of approximately parallel nanofibers, (c) Steps to form nanofiber threads from assembly, (d) A method of recovering nanofiber yarn from an assembly, comprising the step of twisting the yarn by rotation of a collector to form a nanofiber ply. (Item 387) A device that manufactures nanofiber twisted yarn. (a) Steps to continuously supply nanofibers to the collector, (b) With the step of rotating the collector to form an assembly of approximately parallel nanofibers, (c) Steps to form nanofiber threads from assembly (d) A device that can be operated to perform a method that includes a step of recovering nanofiber yarn from an assembly, wherein the yarn is twisted by rotation of a collector to form a nanofiber ply. (Item 388) The method of item 386 or 387, further comprising the step of flowing gas to continuously transport the nanofibers to the collector. (Item 389) The method of item 386 or 387, further comprising the step of winding the nanofiber twisted yarn around the yarn package. (Item 390) A device that contains an array of aligned conductive channels: (a) The conductive channel can be manipulated to directionally transport species selected from the group consisting of electrons, ions, phonons, and combinations thereof. (b) A device provided by nanofibers in which the conductive channel is selected from a group consisting of ribbons, sheets, threads and combinations thereof. (Item 391) Item 390 device (a) The device is involved in the transport of electrons (b) The device further comprises an electrical contact, which brings an electric current through a conductive channel. (i) Due to the nanofibers, the current has very low noise (ii) The current may be of the type selected from the group consisting of alternating current, pulsed current, direct current, and combinations thereof. (c) A device in which the device can be operated for use as at least one of a conductor, a transmission line, a register with a low thermal resistance factor, and a heater. (Item 392) The device of item 391 (a) The device is involved in the directional transport of electrons (b) The current flowing through the aligned conductive channels is very anisotropic, the ratio of the current along the channel to the current perpendicular to the channel is at least about 10 or more, and the anisotropy is the aligned conductive channel. The device given by the alignment of. (Item 393) The device of item 391 (a) The device is operable and can be used as a sensor. (b) The sensor detects changes in current flowing through the conductive channel by an external detector that interacts with at least one of the conductive channels. (c) The sensor is a type of device selected from the group consisting of chemical sensors, environmental sensors, radiation sensors, and combinations thereof. (Item 394) The device of item 393, wherein the device sensor is an environmental sensor capable of sensing environmental conditions selected from the group consisting of temperature, pressure, and combinations thereof. (Item 395) The device of item 394 (a) The sensor is a matrix sensor and (b) The matrix sensor can detect the position and (c) The matrix is a device provided by a combination of overlapping orthogonally arranged sheets of at least two conductive channels. (Item 396) Item 390 device The device provides an electromagnetic (EM) shield, the EM shield of which is the type selected from the group consisting of reflective, absorbent, permeable, and combinations thereof. (Item 397) Item 390 device that provides antenna functionality for electromagnetic (EM) irradiation. (Item 398) The device of item 396 (a) The device is integrated with a display device that has a screen. (b) An optically transparent nanofiber sheet coats the screen of the display so that EM radiation emitted by the display device is blocked from passing through the screen. (c) A display device is a device that includes a display element selected from the group consisting of LCDs, LEDs, OLEDs, FEDs, cathode ray tubes (CRTs), and combinations thereof. (Item 399) Item 390 device (a) The device can be operated for heat transfer via phonon and electron transport. (b) The device further comprises a thermal sink that is in thermal contact with the conductive channel. (c) A device to which a heat source can be applied to the device by means selected from the group consisting of direct thermal contact, EM radiation, light rays, particle beams, and combinations thereof. (Item 400) A device of item 399, which can be operated as a thermal imaging matrix bolometer, the thermal imaging matrix bolometer being operable to measure temperature distribution over a wide range from room temperature to 3000 ° C with high sensitivity and high resolution. (Item 401) (a) Steps to provide oriented nanofibers in a form selected from the group consisting of ribbons, sheets, threads and combinations thereof. (b) A method comprising the step of using the oriented nanofibers as an array of conductive channels for directional transport of species selected from groups consisting of electrons, ions, phonons and combinations thereof. (Item 402) The step of using the oriented nanofibers comprises transporting electrons, and the method further comprises the step of providing electrical contact to the oriented nanofibers to establish an electric current through the oriented nanofibers. A method of 401, wherein (a) the current has low noise characteristics and (b) the current is the type selected from the group consisting of alternating current, direct current, and combinations thereof. (Item 403) The method of item 401, wherein the step of using the oriented nanofibers comprises transporting heat and temperature by transporting phonons, the method further comprising providing a thermal sink that is in thermal contact with the oriented nanofibers. .. (Item 404) The step of using the oriented nanofibers comprises shielding EM radiation, such shielding comprising a type selected from the group consisting of reflectivity, absorbency, permeability, and combinations thereof, item 401. the method of. (Item 405) The step of using the oriented nanofibers establishes at least one sensor, the sensor of which is the type selected from the group consisting of chemical sensors, environmental sensors, radiation sensors, and combinations thereof. 401 methods. (Item 406) (a) Cathodes containing nanofibers in a form selected from the group consisting of threads, ribbons, sheets and combinations thereof. (b) A device comprising an anode in which a region of low gas pressure separates from the cathode. (Item 407) A device of item 406 that further includes a first structure type that includes nanofiber stranded yarn as a major component and is operable for use as a field emission cold cathode in the shape relative to the anode, said shape from the yarn tip. A device selected from the group consisting of a vertical type for electron emission, a horizontal type for emission from the side of the yarn, and a combination thereof. (Item 408) (a) The cathode contains nanofibers in the form of threads (b) The device of item 407, in which the yarn is woven into a supporting fabric matrix to provide a cathode fabric assembly in which the current density can be operably controlled by the density and shape of the fabric. (Item 409) (a) The cathode contains nanofibers in the form of threads (b) The device of item 407, wherein the device incorporates a thread-reinforced nanofiber sheet containing nanotubes selected from the group consisting of multi-walled carbon nanotubes, single-walled carbon nanotubes, and combinations thereof. (Item 410) (a) The cathode contains nanofibers in the form of threads. (b) The device of item 407, wherein the device further comprises an optically transparent nanofiber sheet as a cathode part, comprising multi-walled carbon nanotubes, single-walled carbon nanotubes, and combinations thereof. (Item 411) It further includes a second structural type that includes nanofibers of the form selected from the group consisting of nanofiber ribbons, nanofiber sheets, and combinations thereof as the main components, and is used in the shape associated with the anode as a field emission cold cathode. A device of item 406 that is operational for. (Item 412) A device of item 411 that further comprises a primary substructure comprising nanofibers in the form of sheets, ribbons, and combinations thereof, wherein the nanofiber sheets and ribbons are optically transparent. (Item 413) A device of item 407, further comprising a second substructure containing twisted yarns with knots of various topologies along the twisted yarn, wherein the emission current can be operably modulated at at least one position of the knots. (Item 414) A device of item 407, further comprising a second substructure containing an array of threads assembled in multiple lap assemblies of various desired shapes, wherein the emission current density and operating voltage are among the lap assemblies. A device that can be adjusted by the number of threads in one superposed assembly and one or both of the superposed assembly geometries. (Item 415) A device of item 407, further comprising a second substructure containing a single yarn. (a) A single yarn with an end is placed perpendicular to the anode and (b) A device in which the end of the thread is capable of handling emitted electrons and creating a dot image at the anode. (Item 416) A device of item 407, further comprising a second substructure, in which the yarn is placed on a plane having a yarn side parallel to the anode, so that electrons are operably emitted from the side of the yarn onto the anode. A device that can create an image of a line. (Item 417) A device of item 407, further comprising a second substructure containing a twisted yarn spirally wound with a pitch around a support wire or cylinder, wherein the pitch is a device whose emission current density can be operably adjusted. (Item 418) The device of item 411, wherein the cathode is optically transparent and is located in front of the anode so that the emitted electrons can move posteriorly from the cathode towards the anode and the anode can be seen through the transparent cathode. .. (Item 419) It is self-modifying in that the electron current density increases with increasing operating time, and the threshold and operating voltage decrease with operating time due to the unwinding of the twisted yarn in a high electric field and the creation of additional nanofiber free ends extending from the body of the yarn. Device of item 407. (Item 420) (a) A cold cathode for field emission containing nanofibers having a shape selected from the group consisting of threads, ribbons, sheets and combinations thereof, wherein the shape is (i) With the steps of arranging the nanofibers aligned in an array with sufficient interfiber connectivity in the array to provide the main assembly. (ii) Steps to pull out the nanofibers as electrode material from the main assembly, With a cold cathode, which is made by a method that includes (b) A device comprising an anode in which a region of low gas pressure separates from the cathode. (Item 421) A method for manufacturing the device of item 420, (a) The following components, i.e. (i) Cathodes containing nanofibers in a form selected from the group consisting of threads, ribbons, sheets, and combinations thereof, and (ii) Anode And the steps to provide (b) A method comprising the step of establishing a low pressure region between the anode and the cathode. (Item 422) The cold cathode contains an optically transparent nanofiber sheet, The device of item 420, where the optically transparent nanofiber sheet contains multi-walled carbon nanotubes. (Item 423) The device of item 420, wherein the cold cathode comprises an optically transparent nanofiber sheet, wherein the optically transparent nanofiber sheet comprises single-walled carbon nanotubes. (Item 424) The nanofibers are SiC nanofibers, MgB₂Nanofiber, carbon-doped MgB₂Nanofiber, WO-tungsten oxide nanofiber, WS₂Nanofiber, Bi nanofiber, binary nanofiber of Group III-V element, Si nanofiber, ZnO nanofiber, selenium nanofiber, fluorinated nanofiber, nanofiber which is a compound of Mo, S and I , And the device of item 420 selected from the group consisting of combinations thereof. (Item 425) The device of item 422, wherein the multi-walled carbon nanotubes are manufactured by a plasma-enhanced chemical vapor deposition method, and the structure of the nanotubes can be controlled by plasma parameters. (Item 426) Can be operated for use as a device of choice from the group consisting of flat panel displays, fluorescent lamps, incandescent lamps, surge protective gas discharge tubes, X-ray generators, microwave generators, and combinations thereof, item 420 Device. (Item 427) A device of item 420 that further comprises a fluorescent coating on the anode, wherein the fluorescent coating can be manipulated to provide light emission. (Item 428) (a) The nanofibers include a sheet wrapped around a transparent capillary. (b) The transparent capillary is configured axially in the device (c) The device of item 420, where the anode and device are cylindrical. (Item 429) The device of item 420, where field emission occurs primarily from the sides of the nanofibers inside the transparent sheet. (Item 430) Cold cathodes are further manufactured by methods that include processing the nanofibers to form new free ends protruding from the surface from the nanofibers, which can be actuated to provide enhanced field emission. The device of item 420. (Item 431) The device of item 430, wherein the treatment step comprises a method selected from the group consisting of plasma treatment, mechanical wear, sonication, thermal annealing, chemical treatment in an oxidizing environment, and combinations thereof. (Item 432) The device of item 420, in which the cathode nanofibers are patterned. (Item 433) A method of patterning nanofiber sheets along their length, which involves photopolymerization; photolithography; electron beam-induced polymer reactions; pressure-induced mass transfer; material deposition. , Removal, and transformation, including liquid treatment, gas phase treatment, and plasma treatment; and patterning techniques selected from the group consisting of combinations thereof. (Item 434) A method for making a nanofiber sheet cold cathode according to item 420, which comprises using periodic patterning of an aligned nanofiber forest array into which nanofibers are spun to make a nanofiber sheet cold cathode. Method. (Item 435) The method of item 434, wherein the periodic patterning comprises providing periodic patterning of a nanofiber forest sequence. (Item 436) The patterning technique is a periodic change of properties selected from the group consisting of nanofiber sheet thickness, nanofiber shear width, nanofiber composition, nanofiber structure, nanofiber length, nanofiber overcoat material, and combinations thereof. The method of item 433, which comprises periodically patterning the nanofiber sheet in. (Item 437) The patterning technique is periodic to give a periodic change in the electrical conductivity for different sections of the nanofiber sheet along the length and width of the nanofiber sheet so as to create a spatially periodic change in the emission current. Item 433 methods, including patterning into. (Item 438) (a) A first electrode that contains nanofibers in a form selected from the group consisting of threads, ribbons, sheets, and combinations thereof. (b) The active layer associated with the first electrode and operability, (c) An optoelectronic device that includes an active layer and a first electrode and a second electrode that is operably associated. (Item 439) (a) The first electrode, which contains nanofibers of a shape selected from the group consisting of ribbons, sheets, and combinations thereof, wherein the shape is (i) With the steps of placing the nanofibers in an aligned array with sufficient interfiber interconnection within the array to provide the main assembly. (Ii) a first electrode manufactured by a method comprising the step of withdrawing the nanofibers as an electrode material from the main assembly, and (b) an active layer operably associated with the first electrode. (c) An optoelectronic device that includes an active layer and a first electrode and a second electrode that is operably associated. (Item 440) The optoelectronic device of item 438 or 439, wherein the first electrode is optically transparent. (Item 441) The optoelectronic device of item 440, wherein the nanofibers are coated with a material selected from the group consisting of low work function metals, single-walled carbon nanotubes and combinations thereof. (Item 442) The nanofibers are electrons in an intertube charge transfer dopant selected from the group consisting of alkali metals and other electron donors for n-type doping, halogens, and other electron acceptors for p-type doping, and combinations thereof. Item 440 optoelectronic device to be doped. (Item 443) The optoelectronic device of item 440, wherein the nanofibers are electronically doped with an in-tube substitution dopant selected from the group consisting of B, N, P, and combinations thereof. (Item 444) The first electrode is impregnated with an active material selected from the group consisting of conductive polymers, different types of nanofibers, different types of nanotubes, semiconductor nanocrystals, quantum dots, quantum rods, organic dyes, and combinations thereof. Item 440 optical electronic device. (Item 445) For use as a device selected from the group consisting of solar cells, photovoltaic detectors, photovoltaic transistors, LEDs, OLEDs, PLEDs, photosensitive FETs, electric pump lasers, and combinations thereof. A photovoltaic device of item 438 or 439 that is operational. (Item 446) 440. The optoelectronic device of item 440, wherein said device is a photovoltaic device and the first electrode can act as a passive anode for the collection of positive charges created in the active layer. (Item 447) 441. The optoelectronic device of item 441, wherein the material is a material with a low work function and the device is a photovoltaic device in which the coated nanofiber electrode can act as a passive electrode to collect negative charges. (Item 448) The optoelectronic device of item 446 or 447, wherein the optoelectronic device is a photovoltaic device that is operable to function as a solar cell. (Item 449) The optoelectronic device of item 446 or 447, wherein the optoelectronic device is a photovoltaic device that can act as a photodetector. (Item 450) 440 optoelectronic devices, wherein said device is a photovoltaic device, the first electrode is capable of acting as a photoactive anode for enhanced light absorption and for light generation of charge carriers. (Item 451) 441. The optoelectronic device of item 441, wherein said device is a photovoltaic device, the first electrode being operable to act as a photoactive cathode for enhanced light absorption and for light generation of a charge carrier. (Item 452) The optoelectronic device of item 440, wherein the nanofibers have a three-dimensional shape and topology with an interface extending to the active layer and penetrate the pores of the nanofiber matrix of the first electrode so that the active layer provides a charge generation network. .. (Item 453) 440. The optoelectronic device of item 440, wherein the first electrode is impregnated with an active substance selected from the group consisting of titanium oxide, zinc oxide, tungsten oxide, and mixtures thereof. (Item 454) The optoelectronic device (a) A reducing electrode in the form of a transparent nanofiber material attached to a non-conductive flexible substrate, wherein the transparent nanofiber material is selected from a group consisting of sheets, threads, and combinations thereof. With the reduction electrode (b) A photoelectron device of item 440, which is a photoelectrochemical, dye-sensitized solar cell comprising a conventional porous titania-containing oxide electrode having a dye. (Item 455) In the photoelectrochemical / photoelectrochemical device of item 454, the dye-sensitized solar cell has an oxide electrode made of a transparent nanofiber material, and the transparent nanofiber material serves as a host material for porous titania and dyes. Photoelectron and photoelectrochemical devices coated with a coating selected from the group consisting of metal oxides and combinations thereof. (Item 456) The dye-sensitized solar cell comprises a coating on the reducing electrode selected from the group consisting of monolayer nanotubes and metals with electrochemical catalytic activity, the coating enhancing the charge exchange reaction with the electrolyte. Item 455 photoelectron / photoelectrochemical device that is operable. (Item 457) Item 440 Photoelectronic device further comprising at least one transparent nanofiber electrode, thereby forming a multi-junction connected photovoltaic device, wherein the transparent nanofiber electrode acts as a separate interconnect layer between single-junction components. .. (Item 458) A transparent nanofiber separation interconnect layer having a first surface and a second surface is further included, and the transparent nanofiber separation interconnection layer is formed on the transparent nanofiber electrode and the active layer so as to function as a charge recombination layer operably. The transparent nanofiber-separated interconnect layer is operably connected and at least partially said to form a double-sided electrode having different work functions on the first and second surfaces of the transparent nanofiber-separated interconnect layer. An optoelectronic device of item 457, coated on the front surface. (Item 459) The optoelectronic device of item 440, wherein the device is an organic light emitting device (OLED), the first electrode comprising an anode for injecting a positive charge into the active layer. (Item 460) The optoelectronic device of item 459, wherein the OLED includes a first layer, a second layer and a third layer in the active layer. (a) The first layer comprises a hole transport layer (HTL), the HTL being disposed around the nanofibers of the first electrode. (b) The second layer contains a radiating zone (EML). (c) An optoelectronic device in which the third layer comprises an electron transport layer (ETL). (Item 461) A method of manufacturing optoelectronic devices (a) Steps to give components including: (i) A self-supporting transparent nanofiber material that is operable for use as a first electrode, said material in a form selected from the group consisting of threads, ribbons, sheets and combinations thereof, and. The material is about 10m²Free-standing transparent nanofiber material with a surface area greater than / g; (ii) Active material layer operably associated with the first electrode; (iii) Active material and second electrode operably associated with the first electrode; and (b) A method, including the steps of assembling components to form an optoelectronic device operably. (Item 462) Item 461, wherein the assembly step includes bottom-up, direct assembly, and the assembly step is (a) A step of depositing the self-supporting nanofiber material in the form of a low-density aligned airgel as a first transparent electrode on a transparent substrate, (b) A step of depositing the active material on top of the first transparent electrode, and (c) A method comprising the step of depositing the second electrode selected from the group consisting of opaque and transparent electrodes on top of the active material. (Item 463) The method of item 462, wherein the transparent substrate is selected from the group consisting of glass, flexible plastic films, elastomeric plastic films, elastomeric fibers and combinations thereof. (Item 464) Item 461, wherein the assembly step includes an upside down assembly step. (a) Step of depositing the second electrode on the substrate, (b) The step of depositing the active material on the upper part of the second electrode, and (c) A group consisting of press lamination, stamping, deposition, and combinations of self-supporting transparent nanofiber sheets in the form of low-density self-contained aligned airgel on top of the active layer as the first transparent electrode. A method that includes a step attached using a more selected method. (Item 465) 464. The method of item 464, wherein the substrate comprises a material selected from the group consisting of silicon wafers and other opaque materials. (Item 466) The method of item 461, in which the self-supporting nanofiber electrode (a) With the steps of arranging nanofibers in an ordered array with sufficient interfiber connectivity to provide the main assembly. (B) and a method manufactured by a method comprising the step of withdrawing the nanofibers as an electrode material from the main assembly. (Item 467) The method of item 466, wherein the orthopedic arrangement comprises a nanofiber forest. (Item 468) The method of item 466, wherein the step of making a self-supporting nanofiber electrode is selected from the group consisting of conductive polymers, different types of nanofibers, quantum dots, quantum rods, organic dyes, and combinations thereof. A method further comprising filling the pores in the nanofiber electrode with a material, said filling step is performed following the step of arranging the nanofibers in an ordered arrangement. (Item 469) The method of item 468, wherein the filling step is performed following the withdrawal step.</p>

For further understanding and benefit of the present invention, the following description, along with the accompanying figures, is provided:<figref num="1">Figure 1 is an optical micrograph showing nanotube fibers pulled out of a nanotube forest while twisting at high speed using the motor in the photo.</figref><figref num="2">Figure 2 shows a scanning electron microscope (SEM) photograph of the integration of the ribbon drawn from the MWNT forest during the drawing and plying process into the plying yarn at two different magnifications (A and B). Then, a forest band with a width of ~ 600 μm formed a nanofiber plying with a diameter of 3.2 μm in the photograph.</figref><figref num="3">Figure 3 shows SEM photographs of carbon MWNT yarns of single yarn (A), twin yarn (B), and quadruple yarn (C), and knit yarn (D) and knot carbon MWNT single yarn (E) of MWNT single yarn. Is shown.</figref><figref num="4">FIG. 4 provides SEM photographs showing single-walled single-walled twisted yarns (bottom) and twin yarns (top) of carbon MWNTs that the twists hold until breakage due to tensile failure occurs.</figref><figref num="5">FIG. 5 is an engineering curve of stress-strain leading to fracture, showing (a) carbon MWNT singles, (b) MWNT carbon nanotube twins, and (c) PVA-infiltrated MWNT singles.</figref><figref num="6">FIG. 6 shows a single-knot SEM micrograph of a twin thread of carbon multi-walled nanotubes having approximately the same diameter as the thread.</figref><figref num="7">Figure 7 shows the hysteresis of the stress-strain curve (strain rate of 1% / min) observed under the conditions of deloading and reloading beyond the 1.5% strain range after pre-mechanical conditioning of the carbon MWNT twins. Is shown.</figref><figref num="8">FIG. 8 shows the energy loss vs. initial strain per cycle under unloading conditions for 1.5% strain (square) and 0.5% strain (circle) cycles for the stress-strain loop of FIG.</figref><figref num="9">Figure 9 shows the effective modulus of the carbon MWNT twin yarn as a function of the stage of the hysteresis cycle, and the effective modulus of thread calculated for the stress-strain loop shown in Figure 7 is for total tensile strain. Is plotted. Here, the circles and squares indicate the effective elastic moduli at the beginning and end of deloading, respectively, and the diamonds and triangles indicate the effective elastic moduli at the beginning and end of reloading, respectively.</figref><figref num="10">Figure 10 shows the relationship between the rate of change in diameter and the rate of change in length during elongation of MWNT twin yarn (upper) and MWNT single yarn (lower), and the symbol used here is a white circle (initial elongation). , Solid rhombus (first stress decrease), solid circle (second stress increase), solid triangle (second stress decrease), and solid square (stress increase until thread breakage), guided by curves to make them stand out. Will be done.</figref><figref num="11">Figure 11 shows a photograph of a spun ribbon of carbon MWNT spirally wound over a hollow capillary tube with a diameter of 1 mm, where it is highly transparent (due to the winding thickness giving a low resistance layer). Is indicated by the readability of the 3/4 point line written on the paper sheet behind the capillary wrapped with the nanotube ribbon.</figref><figref num="12">FIG. 12 shows a single-knot SEM micrograph of a single-walled twisted yarn of MWNT, with the relevant yarn volumes at the entrance and exit of the knot removed from the knot. And the body of the knot is given a region with a density difference that can be used as a selective region for infiltration and reaction, and the stray nanotubes that migrate from the knot and other regions of the knot in the photo are sometimes chemical. Can be removed (for example, letting a thread pass through an open flame). And if applications such as field emission are desired, these stray nanotubes can be selectively increased to different regions of the yarn by chemical or mechanical treatment, including chemical treatments that result in nanofiber breakage. Can be done.</figref><figref num="13">Figure 13 shows a single-knot SEM micrograph tied with a single MWNT twin so that the knot contains a second MWNT twin, such as initially between independent threads. The intersection can be used as an electrical junction and a microfluidic junction, and the degree of interaction of the two threads (electrical contact resistance and resistance to mixing of microfluidic) can be changed by tightening the knots.</figref><figref num="14">Figure 14 shows a SEM micrograph of CVD-manufactured coiled carbon nanofibers useful for the production of highly stretchable nanofiber threads.</figref><figref num="15">Figure 15 shows a SEM micrograph of a 280 micron high forest cross section of aligned crimped nanofibers produced by the CVD process.</figref><figref num="16">FIG. 16 is a schematic drawing of a woven structure that provides a docking site for a functional device (eg, a substrate-detachable electronic chip).</figref><figref num="17">FIG. 17 is a photograph of a MWNT spinning ribbon deposited on one side of a microscope slide to produce a transparent conductive sheet, with the trademark printed on a blank sheet underneath the electrically conductive sheet.</figref><figref num="18">FIG. 18 is a photograph of a twin-wound twisted yarn of MWNT yarn electrically heated to an incandescent state in a chamber in an inert atmosphere.</figref><figref num="19">FIG. 19 is a line drawing illustrating a preferred spinning system for producing MWNT yarns according to some embodiments of the present invention, by which a ring, traveler, or cap that significantly increases tension in the yarn. It is shown how the yarn is formed without the need for.</figref><figref num="20">FIG. 20 is a schematic view showing details of a substrate holder in which six substrates coated with nanofibers on both sides may be selectively installed in some cases.</figref><figref num="21">Figure 21 is a photograph of a 3.4 cm wide, meter long, free-standing MWNT sheet manually pulled from an nanotube forest at an average speed of 1 m / min, where the transparency of the sheet is behind the MWNT sheet. Illustrated by the visibility of the Nanotech Institute trademark.</figref><figref num="22">Figure 22 is a scanning electron microscope (SEM) image of the forest plane viewed at a 35 degree angle, capturing the MWNT forest being pulled out onto a sheet.</figref><figref num="23">Figure 23 shows a SEM micrograph showing a 90 degree joint swirl of MWNT in the forest to form a tough carbon nanotube sheet.</figref><figref num="24">FIG. 24 shows the normalized resistance value R (T) of the sheet measured in vacuum with respect to R (300K) with respect to temperature. According to the inset, the temperature dependence of sheet resistance is almost the same before (solid rectangle) and after (white circle) densification in the forest-drawer direction of the forest-drawer sheet, and the densified forest-drawn sheet. It is shown to be almost identical in the direction perpendicular to (diamond) and to the filtration-manufactured sheet of MWNT grown in the forest (solid circle).</figref><figref num="25">FIG. 25 shows the light transmittance for wavelengths of MWNT single yarn sheets before and after densification for both polarized and unpolarized light. The arrows indicate the position of the data for the non-density sample to the data for the densified sample.</figref><figref num="26">Figure 26 shows the noise power density (measured with a 10 mA bias in air) vs. frequency for a MWNT densified forest-drawing sheet (white circle) and that of a normal MWNT filtration-manufactured sheet (solid circle). , And those of SWNT sheets (solid rectangles) with the same 40Ω resistance are shown in comparison. The dotted line depends on the frequency (f) 1 / f^αWhere α is 0.98 ± 0.04, 0.97 ± 0.02, and 1.20 ± 0.02, respectively. Lower limit of noise power at temperature T (4k)_BProduct of T and sample resistor R, where k_BIs the Boltzmann constant) is indicated by the horizontal dotted line.</figref><figref num="27">FIG. 27 is a SEM micrograph of a two-dimensional reinforced structure produced by stacking four nanotube sheets with a 45 degree offset between the next sheets.</figref><figref num="28">FIG. 28 is an SEM image showing the branching of raw fibers inside a densified sheet manufactured in the solid state of MWNT.</figref><figref num="29">FIG. 29 shows measurements of mechanical properties of MWNT sheet cuts as drawn from a single original sheet stacked on top of each other so that they have a common nanotube orientation direction. (A): Engineering stress vs. strain data, showing that the change in maximum stress is surprisingly small for samples containing different numbers of sheets stacked on top of each other. (B): The maximum force for the sample test of (A) and the corresponding strain are shown as a function of the number of laminated sheets.</figref><figref num="30">FIG. 30 is a photograph showing that the as-pulled nanotube sheet supports millimeter-sized droplets of water, orange juice, and grapefruit, where the masses of the millimeter-sized droplets are in contact. It reaches 50,000 times the mass of the nanotube sheet.</figref><figref num="31">FIG. 31 shows a self-supporting, non-dense MWNT sheet (16 mm × 23 mm) used as a flat incandescent light source that emits polarized light, where the background colors of the non-heated sheet (A) and the incandescent sheet (B). Is different due to the reflected incandescent light from the white paper sheet behind the light source.</figref><figref num="32">Figure 32 shows the spectral radiance in the directions parallel (||) and perpendicular () to the withdrawal direction of the non-dense MWNT sheet after applying 2.5% inelastic elongation in the initial withdrawal direction. Shown. The inset shows this data on a half logarithmic scale. The underlying solid line (mostly obscured by coincidence with the data points) is a data fit assuming blackbody radiation at T = 1410K.</figref><figref num="33">FIG. 33 is a photograph of a MWNT sheet sandwiched between 5 mm-thick plexiglass plates and welded together by microwave induction heating. At this time, electrical conduction was achieved by this welding method. The properties, nanotube orientation, and transparency of the nanotube sheet are preserved.</figref><figref num="34">Figure 34 provides a picture of an electrically conductive and microwave-absorbing appliqué containing a non-dense MWNT sheet attached to a transparent adhesive tape (Scotch tape from 3M), where the transparency of the appliqué. Is indicated by the visibility of the trademark and "UTD" printed on a blank sheet of paper under the appliqué. In the lower photo, the appliqué is folded (and held together using a paper clip) for experiments showing that the resistance of the sheet is largely unaffected by folding.</figref><figref num="35">Figure 35 shows that 100% elongation of the silicone rubber sheet to which the MWNT sheet is attached causes almost no change in the resistance of the MWNT sheet (without correction for the geometrical shape change when transitioning from the extended state to the contracted state). Is shown.</figref><figref num="36">FIG. 36 is a photograph of an organic light emitting diode (OLED) using a MWNT sheet manufactured in a transparent solid state as a hole injection electrode.</figref><figref num="37">Figure 37 shows that MWNTs in a MWNT sheet on one substrate can produce printed images ([UTD nanotech]] on another substrate by mechanical transfer, which is the parenchyma of nanotube orientation. The photo on the left shows the MWNT sheet attached to the substrate (non-porous paper) after the transfer process, and the right side shows the normal writing paper with the transferred image.</figref><figref num="38">FIG. 38 schematically illustrates a method for simultaneously and independently changing the speed of plying and winding with respect to a yarn using a single motor. The method can be performed by applying minimal tension to the spun yarn, so if the yarn diameter is very small, if the low strength yarn is processed before the subsequent strength enhancement, or if it is highly elastically deformed. It is especially useful when low-strength yarns are required.</figref><figref num="39">FIG. 39 shows an optical micrograph of a multi-walled nanotube yarn spirally wound onto a bobbin (5 mm diameter plastic tube) between a carbon nanotube forest and a yarn-based yarn spinning.</figref><figref num="40">FIG. 40 shows an optical micrograph of a CNT-wool composite yarn in which CNT fibers and wool fibers are introduced between the spinning of twisted yarns.</figref><figref num="41">In FIG. 41, a VV configuration (parallel polarization with respect to incident light and Raman signal) is used for a stack of four as-extracted sheets, all of which have the same orientation, and the nanotubes are extracted. Raman data parallel (||) or perpendicular () to the direction illustrates the high degree of orientation of the nanotubes in the nanotube sheet.</figref><figref num="42">FIG. 42 shows an optical micrograph of a MWNT twin yarn (composed of a single yarn of 12 μm) inserted into a normal woven fabric consisting of melt-spun filaments with a diameter of 40 μm.</figref><figref num="43">FIG. 43 schematically illustrates a rotating spinner (spinning frame) that converts nanofibers such as carbon nanotubes into twisted yarns.</figref><figref num="44">FIG. 44 schematically illustrates a device for densifying carbon nanotube yarns using spinnerets that introduce false twists, which means there is no net twist. An optional method (by syringe pump) for inserting additives for additional densification is also drawn.</figref><figref num="45">FIG. 45 provides details of the spinneret of FIG. 44 for introducing false twist.</figref><figref num="46">FIG. 46 schematically illustrates a spinning machine using false twist spun caps used to increase the strength and densification of nanotube yarns prior to the introduction of net twists (also known as true twists). To.</figref><figref num="47">Figure 47 shows the dependence of electrical resistance on twist levels (in units of counts / meter) on MWNT yarns spun in the solid state.</figref><figref num="48">FIG. 48 shows the dependence of the ultimate tensile stress as a function of the helix angle (relative to the yarn direction) for the MWNT yarn spun in the solid state. Here, the white circles correspond to the case where there is no pretreatment, and the white squares are initially liquid infiltrated to avoid a too drastic decrease in nanotube thread strength due to the decrease in twist angle, and are densified by liquid evaporation. Correspond to the case.</figref><figref num="49">FIG. 49 shows the dependence of the break strain as a function of the twist angle (relative to the yarn direction) of the sample yarn with respect to the MWNT yarn spun in the solid state of FIG. 48.</figref><figref num="50">Figure 50 shows the dependence of extreme tensile stress on low and high twist yarns as a function of yarn diameter.</figref><figref num="51">FIG. 51 shows the dependence of break strain on low and high twist yarns as a function of yarn diameter.</figref><figref num="52">According to FIG. 52, (a) thread A: 26000 times / m twisted clockwise, and (b) thread B: first clockwise twisted 26000 times / m and then untwisted. SEM images of those with the same counterclockwise twist introduced to do so are compared.</figref><figref num="53">FIG. 53 shows the process by which an nanotube sheet is pulled out, attached to a substrate film, immersed in a liquid to evaporate the liquid to a high density, and then wound onto a mandrel.</figref><figref num="54">FIG. 54 shows how an nanotube sheet is pulled out, attached to a substrate film, densified using vapor exposure, and then collected on a mandrel.</figref><figref num="55">FIG. 55 shows how the nanotube sheets are laminated between the films.</figref><figref num="56">FIG. 56 compares SEM micrographs of the growing substrate against spinnable and non-spinnable nanotube forests (after removing the nanotubes), and the small diameter holes on the growing substrate correspond to the growth sites of the MWNTs.</figref><figref num="57">Figure 57 gives an SEM micrograph showing that PVA infiltration does not split the structure of the MWNT single yarn base.</figref><figref num="58">FIG. 58 is a SEM micrograph showing about 20 MWNT single yarns stacked together to produce 20 yarns having a diameter approximately equal to the diameter of human hair.</figref><figref num="59A">Figures 59A-C schematically illustrate the components and successive steps in the process of making a matrix-addressable calorimeter particle detector. A) draws a free-standing nanofiber sheet conductor with high anisotropic electrical and thermal conductivity as a result of the nanofiber orientation; B) draws two nanofiber sheet conductors (A). (Of the type shown in) is attached extending from the opposite side of the frame, resulting in a frame containing an array of orthogonal nanofiber sheet conductors and metal electrode pads with a rectangular central opening. .. The metal electrode pad is coated with a thin film of temperature sensitive material. According to C), two orthogonally arranged nanofiber sheets attached to opposite sides of the frame are drawn according to some embodiments of the present invention.</figref><figref num="59B">Figures 59A-C schematically illustrate the components and successive steps in the process of making a matrix-addressable calorimeter particle detector. A) draws a free-standing nanofiber sheet conductor with high anisotropic electrical and thermal conductivity as a result of the nanofiber orientation; B) draws two nanofiber sheet conductors (A). (Of the type shown in) is attached extending from the opposite side of the frame, resulting in a frame containing an array of orthogonal nanofiber sheet conductors and metal electrode pads with a rectangular central opening. .. The metal electrode pad is coated with a thin film of temperature sensitive material. According to C), two orthogonally arranged nanofiber sheets attached to opposite sides of the frame are drawn according to some embodiments of the present invention.</figref><figref num="59C">Figures 59A-C schematically illustrate the components and successive steps in the process of making a matrix-addressable calorimeter particle detector. A) draws a free-standing nanofiber sheet conductor with high anisotropic electrical and thermal conductivity as a result of the nanofiber orientation; B) draws two nanofiber sheet conductors (A). (Of the type shown in) is attached extending from the opposite side of the frame, resulting in a frame containing an array of orthogonal nanofiber sheet conductors and metal electrode pads with a rectangular central opening. .. The metal electrode pad is coated with a thin film of temperature sensitive material. According to C), two orthogonally arranged nanofiber sheets attached to opposite sides of the frame are drawn according to some embodiments of the present invention.</figref><figref num="59D">Figure 59D shows a one-sheet calorimeter particle detector using a thin iron wire (5911) and a constantan high-sensitivity thermocouple.</figref><figref num="60">FIG. 60 schematically illustrates an anisotropic resistor with a low temperature coefficient of resistance, which is insulating to give the desired resistance value depending on the number of turns deposited or utilized on a flat insulating substrate. It is made by wrapping it on a cylindrical substrate.</figref><figref num="61">FIG. 61 schematically illustrates the nanofiber sheets arranged in a transparent electromagnetic (EM) shield configuration, which is flexible, electrically conductive, as obtained by the nanofiber sheets drawn out in a solid state. , Transparency, radio frequency and microwave absorption, and bichromaticity can be used advantageously.</figref><figref num="62A">Figure 62A schematically illustrates a gas sensor using carbon MWNT nanotube sheets, the sensitivity of which is enhanced by the use of SWNT sedimentary layers. Although the MWNT seats are outlined here using a series of parallel lines, it should be recognized that there is some degree of side connectivity to the MWNT seats and this degree of side connectivity. Both increases the mechanical robustness of the sheet and reduces the anisotropy of the sheet.</figref><figref num="62B">Figure 62B illustrates that exposure of SWNT sheets to either benzene or alcohol vapors causes significant changes in resistance, which confirms the feasibility of the device concept.</figref><figref num="63">FIG. 63 schematically illustrates a transparent antenna made of oriented nanofiber sheets, optionally laminated on a flexible or elastic substrate.</figref><figref num="64">FIG. 64 schematically illustrates a nanofiber sheet-based heat exchanger for dissipating excess heat from a microelectronic chip. The nanotube sheets are connected by a laminate to a heat sink, shown as a copper plate.</figref><figref num="65">Figure 65A-D shows an SEM image depicting the cathode of different types of carbon nanotube yarns manufactured using early withdrawal methods from a forest of carbon tubes: (A) Twisted single yarn. (B) Knotted twin yarn. (C) Many threads knotted together. And (D) a single thread spirally wound around a glass capillary.</figref><figref num="66">Figures 66A and 66B schematically illustrate (A) the geometry of a cathode that is flat in the horizontal axis and (B) a vertical single-terminated cathode for field emission from MWNT strands, respectively.</figref><figref num="67">Figure 67 is a typical current-voltage (IV) plot of field emission from a vertically single-terminated geometric MWNT yarn. A high voltage (2 kV) pulse was pre-applied to lift the yarn vertically in a short time (1 ms).</figref><figref num="68">FIG. 68 shows the spectrum of light emitted from the end of the twisted single yarn of the MWNT yarn and its suitability for Planck's perfect blackbody radiation law (solid line). At high currents, this light emission from the nanotube thread is accompanied by electron emission. The inset shows a photograph of a light source that emits incandescent light that appears at the tip of the carbon nanotube thread when a high current is used.</figref><figref num="69">FIG. 69 shows the current vs. applied voltage for electron emission from the twisted side of the multi-walled carbon nanotubes. A decrease in rising voltage is confirmed as a result of the hysteresis behavior during the first voltage cycle, indicating that this initial cycle improves electron emission.</figref><figref num="70">Figures 70A and 70B are images of a phosphor screen showing the radiation uniformity of multi-walled carbon nanotubes in a horizontal geometric shape (ie, emitted laterally with respect to the sides of the nanotube thread). The image was taken with a 1 mm gap between the cathode and the phosphor screen anode. The voltages applied to the images A and B were negative pulse voltages of 1.5 kV and 3 kV, respectively.</figref><figref num="71">FIG. 71 is a phosphor screen image showing a numerical representation of alpha patterned based on electron emissions from multi-walled nanotube threads in a flat, patterned geometry. The image was taken with a 1 mm gap between the cathode and the phosphor screen anode. A negative 3 kV pulse voltage was applied to the cathode. The pulse repetition rate was 1 kHz and the duty cycle was 1%.</figref><figref num="72">FIG. 72 schematically illustrates a nanofiber twisted yarn based on some embodiments of the present invention, in which field emission of electrons occurs predominantly from the side of the nanofiber yarn. Nanotubes and bundles of nanotubes extend laterally from the sides of the yarn, providing amplified field emission through enrichment of the electric field lines. Such laterally oriented nanotubes and bundles of nanotubes concentrate the field lines (indicated by the arrows emanating from the anode), which enhances field emission.</figref><figref num="73">FIG. 73 schematically illustrates field emission from the end of electrically conductive nanofiber yarn enhanced by untwisting of the end of the nanofiber twisted yarn in a high electric field, based on some embodiments of the present invention. To. Termination emission of this type of nanofiber yarn is particularly suitable for use as a point-type electron source.</figref><figref num="74-1">Figures 74A and B show SEM micrographs at two different magnifications (A and B) of the yarn rewind during the field emission period. Fluffy threads are formed in the threads by the ends of a large number of nanofibers, and such tips are particularly suitable for enhancing the field emission of electrons.</figref><figref num="74-2">FIG. 74C schematically illustrates the formation of fluffy nanofiber yarns as a result of the electric field effect in the yarn region closest to the anode. The illustrated nanofiber yarn is spirally wound around a wire or cylindrical capillary.</figref><figref num="75">Figure 75A-D is a phosphor screen depicting light emission from a cathode based on both knotless (A and B) and knotted (CD) nanofiber threads in a horizontal geometry. The image above. In the case of the photograph, field emission is suppressed and observed at the knotted portion of the cathode yarn, which is used to pattern the electron emission from the nanofiber yarn cathode.</figref><figref num="76">FIGS. 76A and 76B are current vs. voltage (A) and current vs. time (B) curves of the cold cathode of the self-improving yarn. This indicates an increase in current density and a decrease in threshold voltage and operating voltage as the operating time increases.</figref><figref num="77">FIG. 77 illustrates the concept of using woven fabrics to support electron emitting nanofiber yarns. There, the two electrically conductive nanofiber yarns are woven orthogonally into another substantially non-electron emitting fabric. This insulating fabric (or a fabric composed of wires without electrically conductive nanofibers) provides flexible support for the electron emitting nanofibers and patterns them in the fabric for electron emission purposes. Can be arranged in a different style. The fabric and any component in the fabric can help dissipate the heat generated, and the current density can be adjusted by varying the density and topology of the fabric structure.</figref><figref num="78">FIG. 78 is a photograph showing an operating phosphorescent lamp in which the electron emitting element is a stranded carbon MWNT. This nanofiber thread cathode is wound around a copper wire located in the center of a glass cylinder.</figref><figref num="79">FIG. 79 schematically illustrates a transparent cold cathode electron emitter with a transparent insulating substrate (7902) or a sheet of carbon nanotubes (7901) supported by a substrate coated with a transparent electrically conductive film. .. Where the contact substrate is insulating, the transparent nanotube sheet is contacted with an electrical contact material. It can be an electrically conductive tape (7903).</figref><figref num="80">Figure 80 outlines the two electron emission pathways from the nanotube sheet: electron emission due to field emission at the ends and sides of the (top) nanofibers, and (bottom) tip (freedom extending from the sheet). Electron emission from the sides of the nanofibers (at the ends) and inside the sheet.</figref><figref num="81">FIG. 81 schematically depicts a non-transparent electron emitter used in a typical instrument configuration for a phosphorescent display or lamp. Here the cathode (8102 electron emitter) is on the back side of the display or lamp, and the light is directed forward exclusively from the phosphorescent screen (8105) on the front side of the display or lamp.</figref><figref num="82">FIG. 82 schematically illustrates an electron emitter used in another normal equipment configuration for a phosphorescent display or lamp. Here the cathode (8202 electron emitter) is behind the display (ie behind the phosphorescent screen 8205), and the charge collector is a transparent ITO film (8204). In this geometry some light is radiated backwards. Based on the reflection from behind the display, the display tray has various problems such as reduction of display contrast and display resolution.</figref><figref num="83">FIG. 83 schematically illustrates the display configuration of the present invention, where the electron emitter (8303) of a transparent nanofiber sheet is on the front side of the display and the light emitted by the fluorescent screen (8305) is on the back anode plate. It is reflected by (8306) and reaches the observer after passing through the cathode (8303) of a transparent nanofiber sheet.</figref><figref num="84">FIG. 84 schematically illustrates how the electron emitter cathode of a transparent nanotube sheet is used to create an effective backlit light source for a conventional liquid crystal display (LCD). The light from the back source is polarized (which is desirable for LCD operation) because the transparent cold cathode acts as a polarizing element due to the presence of highly oriented nanotubes in the nanotube sheet.</figref><figref num="85">FIG. 85 depicts a polymeric light emitting diode (PLED) that uses a sheet of densified transparent carbon nanotubes (CNTs) instead of indium tin oxide (ITO), which is typically used as an anode. Due to the flexibility of the carbon nanotube sheet, this PLED may be highly flexible if the substrate is flexible.</figref><figref num="86">FIG. 86 depicts an organic light emitting diode (OLED) that uses a sheet of carbon nanotubes as the anode. Like the PLED, the device has an active low molecular weight organic layer deposited on the top surface of a densified transparent nanotube sheet. Due to the flexibility of the carbon nanotube sheet, this PLED may be highly flexible if the substrate becomes flexible.</figref><figref num="87">Figure 87 depicts a PLED by constructing a stacking scheme starting with the cathode layer and following the deposition of organic / polymeric functional layers. The final layer is a carbon nanotube sheet (anode), which is placed on top of the device by stamping means from another substrate or by laying over the device of the self-supporting nanotube sheet.</figref><figref num="88">FIG. 88 depicts the stacking structure shown in FIG. 87 on a silicon wafer for an active matrix OLED. Silicon wafers can include aluminum / calcium contact pads or transistors. The polymer layer is deposited first, followed by the anode of the nanotube sheet on top.</figref><figref num="89">Figure 89 depicts a transparent PLED that uses a carbon nanotube sheet for both the anode and the cathode. As a result, both electrodes and the device itself are transparent. The device can be built on a flexible / elastic substrate, which can achieve the ultimate goal of a flexible and transparent display.</figref><figref num="90">FIG. 90 illustrates a solar cell or photodetector based on a ribbon of carbon nanotubes as an upper transparent conductive electrode according to some embodiments of the present invention.</figref><figref num="91">FIG. 91 illustrates a solar cell or photodetector based on a ribbon of carbon nanotubes as a bottom transparent conductive electrode according to some embodiments of the present invention. The SEM image of the electrode portion of the carbon nanotube ribbon is also shown on the left, rotated 90 degrees from its placement in the device.</figref><figref num="92">FIG. 92 illustrates a solar cell or photodetector based on a ribbon of carbon nanotubes as top and bottom transparent conductive electrodes according to some embodiments of the invention.</figref><figref num="93">FIG. 93 illustrates a connected solar cell or photodetector based on a ribbon of carbon nanotubes as the upper transparent conductive electrode.</figref><figref num="94">FIG. 94 illustrates an example of the spectral sensitivity of a polymeric solar cell, demonstrating additional functionality such as enhanced light absorption of the charge collector by carbon nanotubes and charge generation in the UV and IR spectral bands. Curve 1 corresponds to the ITO anode, curve 2-4 corresponds to the carbon nanotube sheet anode, and curve 5 corresponds to the carbon nanotube sheet anode coated with a very thin Au / Pd layer.</figref><figref num="95">FIG. 95 is based on a photoactive bulk donor acceptor of conjugated polymer / fullerenes, in which the anode (hole collector) of a transparent nanotube sheet and a nanolinked polymer / nanotube wire as a photoactive electron collector are heterojunctioned. The plastic solar cells are outlined. The inset shows the hole transfer from the conductive polymer chain into the nanotubes in the anode of the transparent nanotube sheet, as well as the electron transfer based on exciton dissociation in the polymer / single layer nanotube system.</figref><figref num="96">FIG. 96 schematically depicts a nanoscale-integrated conjugated polymer / nanotube composite inside 100 nm-scale (on average) pores inside the porous structure of a transparent nanotube sheet. The holes photogenerated in the filled pores are collected on the layered nanotubes inside the polymer's charge collection length (about 100 nm), as indicated by the arrows.</figref><figref num="97">FIG. 97 shows the current vs. voltage curve of a polarization sensitive photoelectric cell utilizing the anode of a transparently oriented carbon nanotube sheet.</figref><figref num="98">FIG. 98 shows an SEM image of a carbon nanotube in which a very thin film (5 nm) Au / Pd is sputtered onto the nanotube. SEM images of uncoated nanotube sheets are shown for comparison.</figref><figref num="99">FIG. 99 schematically illustrates a transparent organic field effect transistor (OFET) with transparent gates, source and drain electrodes and active channels of organic or polymeric semiconductors made of carbon nanotubes. The transparency of this device allows optical modulation of source-drain current, which is useful for optical chip-to-chip information transfer.</figref><figref num="100">FIG. 100 is a schematic diagram showing the basic structure of a dye-sensitized solar cell (DSC) of the prior art, in which a nanofiber sheet can be used as an anode.</figref><figref num="101">FIG. 101 schematically illustrates a novel configuration for a dye-sensitized solar cell. Here, the usual anode of the DSC is replaced with a transparent nanofiber sheet, ribbon, or thread according to an embodiment of the present invention. Cathodes are also made of clear nanofiber sheets, ribbons, or threads coated with nano-level pore titania (instead of traditional ITO).</figref><figref num="102">FIG. 102 shows an SEM image of a single-walled carbon nanotube deposited from a liquid on a transparent sheet of multi-walled carbon nanotubes made using a solid-state sheet-making method or an embodiment of the invention.</figref><figref num="103">FIG. 103 illustrates a multi-junction solar cell (tandem solar cell). A transparent top electrode (10301) in it, and one or more transparent interconnect electrode sheets inside, increase energy extraction efficiency through extending the extraction light to a wider area of the solar light spectrum. It will be possible.</figref><figref num="104">FIG. 104 schematically illustrates a fuel cell based on carbon nanotube yarn.</figref><figref num="105">FIG. 105 schematically illustrates a heat pipe based on carbon nanotube yarn.</figref><figref num="106">FIG. 106 schematically illustrates an apparatus for continuously spinning carbon nanotubes and other nanofibers into twisted yarns. Two motors are used in it to wind the yarn onto the ply and bobbin. The relative rotational speeds of these motors determine the number of twists applied per yarn length.</figref>

Detailed description of preferred embodiments Embodiments of the invention described herein provide novel manufacturing methods, object configurations, and applications for nanofiber threads, ribbons, and sheets with very useful properties. For example, the carbon nanotube threads of the present invention offer the following unique properties and a combination of unique properties: (1) toughness comparable to the fibers used in bulletproof vests, (2) resistance to breakage at knots ( In contrast to the sensitivity of Kevlar® and Spectra® used in bulletproof vests to knotting), (3) high levels of electrical and thermal conductivity, (4) high levels of reversible energy absorption, (5) Break strain is up to 13% compared to a few percent break strain in other fibers of the same toughness, (6) Very high resistance to creep, (7) At 450 ° C in air Retaining intensity even when heated for 1 hour, and (8) having very high radiation and UV resistance even when irradiated in air.

In addition, the inventors (ie, Applicants) can spin these nanotube yarns as 1 μ diameter yarns (or smaller or larger diameter yarns), and twin yarns, quadruple yarns, and more multi-walled yarns. Indicates that the yarn is arbitrarily twisted to produce yarn. In addition, the inventors show that new yarns with the above properties can be spun using either carbon SWNTs or carbon MWNTs, and that the latter is much cheaper to manufacture than the former.

The embodiments of the invention also provide the manufacture of nanofiber sheets of any large width at a commercially useful rate. These sheets are optically transparent and weigh more than the strongest steel sheets and Mylar® and Kevlar® sheets currently used in ultra-lightweight aircraft due to their high weight strength. Has strength.

The important point is how the inventors can use this technique to manufacture various threads, sheets, and ribbons in various nanofibers, and the threads, sheets, and ribbons of these manufactured nanofibers. It also teaches how ribbons are applied.

For the purposes of describing embodiments of the invention most efficiently and clearly, nanofibers are defined herein as fibers or ribbons with a maximum thickness of less than 100 nm perpendicular to the fiber axis.

Since the nanofibers, which can be the smallest for a particular system, form bundles and aggregates of bundles, which also fall under the nanofiber definition classification above, we describe this result herein. Nanofibers are defined as the smallest diameter nanofibers whose individual properties are importantly related to any of the pretreated array assemblies or manufactured sheets, ribbons, or thread structures.

Similarly, the terms knitted, bladed, and woven are indistinguishable, unless otherwise indicated. The reason for ignoring differences in these terms herein is that statements made for any of these terms are generally generally applicable to all of these and similar terms. Similarly, the term two stacked and twisted, and similar terms are used as equivalents for the twisted yarn (ie, stacked).

The problem of spinning nanofibers into twisted yarns in the present invention is a miniaturization of the prior art related to ordinary spinning in which about 1000 superpositions are successfully made using twisted yarns in order to give a specific geometric shape. Optionally preferred, the maximum total number of twists applied in one direction per unit fiber length for twisted yarn of diameter D is at least about 0.06 / D, and significant components for nanofibers are (i) less than about 500 nm. The maximum width of (ii) the minimum length to width is at least about 100, and (iii) the ratio of the nanofiber length to the circumference of the thread is greater than about 5.

In order to produce nanotube sheets and ribbons by the pull-out method in the solid state, selectively preferred, the key components for nanofibers are (i) maximum width less than about 500 nm, (ii) length vs. width. The minimum ratio is at least about 100.

The net twist count is defined as the total twist introduced during all processing from the initial fiber assembly to the intended product. The process that results in untwisting is included in the assessment of the net number of twists. Selectively preferred for twisted yarns, the maximum total number of twists in one direction (without compensating for possible twists in the opposite direction) is at least 0.06 / D. Optionally, the net number of twists (defined as corrected for the number of yarn twists applied in the opposite direction) for the nanofiber yarn can be varied from about zero to about 0.12 / D turns for some applications. At least 0.18 / D for other applications. Especially for applications where high deformability and low yarn strength without breakage are required (eg, yarn actuators where the working material is mainly absorbed into the yarn), the net number of yarn twists is It is preferably 0.18 / D or more.

For the purposes of the present invention, false twists are defined herein as twists in one direction, followed by twisting in essentially equal numbers of twists in opposite directions, resulting in essentially a net number of twists. It becomes zero. The definition herein is by simply twisting at an intermediate position in the yarn (resulting in the introduction of twisting on the side with the twisting position and the automatic substantial removal of twisting on the opposite side of the twisting position). , Or whether the untwisting of the original twist by multiplying the first twist at the end of the yarn and the subsequent equal number of twists for the same yarn end in opposite directions introduces a net number of twists close to zero. Applies to.

We distinguish between ribbons and ribbon-shaped threads (also referred to as threads) by defining ribbons as having a width of at least 1 mm.

For the purposes of drawer-based manufacturing methods, we define preliminary major and major nanofiber assemblies. The preliminary main assembly of nanofibers is at least a nearly parallel assembly of nanofibers (ie oriented nanofibers), which is an oriented nanofiber yarn, a twisted yarn of nanofiber yarns (a false twisted yarn with little net twist). Including), nanofiber ribbons, or subject to substantial changes in the orientation of the nanofibers during the manufacturing process of the nanofiber sheet. The main assembly of nanofibers is an array of oriented nanofibers or a nanofiber array that focuses in a certain orientation direction, where the withdrawal direction for the formation of threads, sheets, or ribbons is the orientation direction of the nanofibers or its orientation. The direction of nanotube orientation that is focused in the direction.

The manufacturing method in the solid state is a method carried out in the absence of the liquid required during the formation of the nanofiber yarn, ribbon, or sheet.

If the required nanofiber properties are clearly not available for carbon nanotubes, then carbon nanotubes are placed in the group of nanofibers that are selectively preferred for embodiments of the invention. It is a nanofiber that can be used. Similarly, the manufacturing method employed to convert the nanofiber array into a sheet, ribbon, or thread is more preferably the solid state manufacturing method of the embodiment of the present invention.

Similarly, a yarn produced by twisting at least one single yarn is interpreted to include a single yarn.

To further understand embodiments of the present invention, the inventors use the term knot herein for both mathematical knots and knots referred to as unknots. Annots can be tied cheaply without the use of robes or thread ends. A useful example of Annot is a draw.

Annot is important. Because it can be manufactured economically, for example during a normal weaving process, and the release of the tie-knot Annot (due to stress at the end of the yarn) dissipates energy (ie, of the yarn) before breakage to any weight of nanofiber yarn. This is because it is a useful method for increasing toughness).

1. Embodiment of the invention of forest-based nanofiber production (a) Twist-based spinning from nanofiber forests One preferred method of the present invention involves spinning based on the twisting of carbon nanotubes from an nanotube forest. It is called a forest because the nanotubes grow like trees that line up approximately parallel to the substrate and have the same height. The nature of the nanofiber forest used for spinning is very important and will be detailed in another section. Most nanofiber forests are unsuitable for the production of twisted yarns, ribbons, or sheets. Other nanofiber forests result in threads or ribbons that are too weak to be used in most applications. For example, Jiang et al. Described the production of very weak, untwisted yarns from their grown nanotube forests (Nature). 419,801 (2002) and US Patent Application Publication No. 20040053780 (March 18, 2004)). These yarns may be weak due to the low functionality of the carbon nanotube forests used and the inability to downscale the twisting method to nanofibers to provide increased strength.

In some important embodiments of the invention, the yarn is simultaneously twisted while being drawn from the nanotube forest. The equipment used in the laboratory to accomplish this twisting process during drawing is shown in Figure 1, and Figures 2A and 2B show nanotubes during drawing from the nanotube forest into nanotubes during spinning. It is an SEM photograph showing that the assembly is made into a thread. In FIG. 1, element 101 is a nanotube forest and has been tuned as described in Example 1. Element 102 is a growth substrate of silicon, element 103 is a ribbon drawn from the forest, and element 104 is a nanotube thread obtained as a result of twisting this ribbon, which is wedge-shaped when viewed in three dimensions. The maximum thickness of the wedge is approximately equal to the height of the nanotube forest. Element 104 is often referred to as the "plying triangle" in the normal weaving process. The overlapping image of both the wedge and the thread of the nanotube is based on the reflection of the mirrored silicon substrate. Element 105 is the end of a small wooden spindle around which nanotube fibers are wound. Element 106 is an adhesive tape that attaches this wooden spindle to the rotating rod of motor 107.

In FIG. 1, the extraction direction is very close orthogonal to the original nanotube direction and parallel to the silicon substrate. Nevertheless, the spinning process is robust enough that the angle between the initial nanotube orientation and extraction is reduced from 90 degrees to almost 0 degrees. This spinning process is easy to accept automation for spinning yarn continuously, but Example 2 is tuned by hand pulling while twisting using a variable speed motor operated below 2000 rpm from the nanotube forest. The warp thread will be described. The diameter of the twisted yarn ranges from less than 1μ to more than 10μ and varies depending on the side wall area in the nanotube forest from which the MWNT yarn is drawn. The combination with a yarn diameter about several hundred times smaller than the nanotube length (about 300 μm) and a large number of twists (about 80,000 times / m) resulted in a yarn with very attractive properties. ..

For twist-based nanofiber extraction and other nanofiber extraction of the embodiments of the present invention for yarn spinning, the nanofibers are extracted essentially simultaneously from the total height of the side wall of the nanofiber forest. Is preferable.

We find that obtaining very useful properties from twisted spinning of such nanoscale fibers requires optimization of a number of conditions, and a number of preferred practices due to these conditions. We have found that the basis of morphology is given. Such conditions are described below.

First, the key components of the nanofibers selectively preferably have a maximum thickness of less than about 500 nm. For circular nanofibers, this maximum thickness corresponds to the nanofiber diameter (if the nanofiber is a nanoribbon, it is the width of the nanofiber). Optionally, more preferably, the key components of the nanofibers should have a maximum thickness of less than about 100 nm. Optionally, most preferably, the key components of the nanofibers should have a maximum thickness of less than about 30 nm. In important components, we say that the components of the nanofiber thickness distribution are powerful enough to have a significant effect on the properties of the yarn.

Second, the nanofibers should selectively preferably have a minimum aspect ratio, i.e. at least about 100 on the sides where the ratio of the length of the nanotubes to the diameter is the thinnest. More preferably, the nanofibers should have a minimum thickness-to-length ratio of at least about 1000 in the thinnest lateral direction. Most preferably, the majority of the weight fraction components of the nanofibers should have an aspect ratio of at least about 10000 at the thinnest flanks.

Third, selectively preferably, the nanofibers in the yarn have a minimum value of the ratio of the nanofiber length to the circumference of the yarn, which is greater than about 5. More preferably, the nanofibers in the yarn have a minimum value of the ratio of the nanofiber length to the circumference of the yarn, which is greater than about 20. Most preferably, the main weight component of the nanofiber has a minimum value of the ratio of nanofiber length to thread circumference greater than about 50.

Fourth, the maximum number of twists that can be put in per yarn length when the twists that may be applied in the opposite direction are uncorrected and the diameter of the twisted yarn is D is selectively preferably at least 0.06 /. It is a D turn. Selectively more preferably for some applications vs. twisted yarn diameter D The maximum number of twists that can be applied is at least about 0.12 / D turns. For several purposes Therefore, selectively and most preferably, the maximum number of twists applied to the twisted yarn diameter D is at least about 0.18 / D turn. The maximum number of twists that can be applied is preferred for some applications. Is preferably 0.06 / D turn or more and 0.12 / D turn or less.

The weight average nanofiber length in the yarn is selectively preferably at least about twice the reciprocal of the number of yarn twists (measured per yarn length).

In addition, selectively preferably at least 20% of the total weight fraction of the nanofibers in the yarn travels from near the yarn surface to the interior of the yarn and at some distance less than about 50% of the nanofiber length. It is selectively preferable to return to the vicinity of the surface. More preferably, the major weight fraction of the nanofibers in the yarn moves from near the yarn surface to the depths inside the yarn and returns to near the yarn surface at some distance less than about 20% of the nanofiber length.

Plying-based spinning methods for nanofiber yarns are preferably achieved by arranging the nanofibers in a substantially aligned or focused manner towards alignment to provide the main assembly. The main assembly is defined as either the nanotubes are arranged approximately parallel to the withdrawal direction or focused in such an alignment as described above. Therefore, depending on the pull-out direction, the nanotube assembly can change from the main assembly to the preliminary main assembly as defined above.

This main assembly can optionally be formed from a precursor assembly such as an nanotube forest, which is either a main assembly or a preliminary main assembly, depending on the withdrawal direction. Nanofibers that focus towards alignment can be formed by pulling these nanofibers out of the nanotube forest. This nanofiber forest is suitable for the formation of the main assembly or as the main assembly and can be on a planar or non-planar substrate. And nanofibers in the forest can be deposited either over substantially the entire surface of the substrate or on only part of the surface. Similarly, different types of nanotubes can be mixed and deposited in different areas of the surface or in the same forest area.

For convenience of spinning nanotube yarns and pulling out ribbons and sheets, the minimum radius of a bent forest substrate relative to the forest occupying area is sometimes at least 10 times the maximum forest height.

The plying process for yarn production can be achieved in the vicinity of the preliminary main assembly (such as a nanofiber forest) (where B is a higher magnification than A, as illustrated in Figure 2). In such cases the rectangular nanotube ribbon is not formed prior to the twisting process. Instead, the rectangular nanotube ribbon can be pulled out of the forest and twisted into the yarn after the rectangular ribbon has been substantially formed.

It is important to note that in Figure 2, the spinning triangles are formed when the nanotubes are pulled out of the forest and are continuously assembled to form a yarn with a substantially circular cross section. The triangular geometry of spinning down to the nanoscale is required for the width of the sidewalls (ie, tips) of the nanofiber forest selected for spinning, the height of the forest, and the spun yarn. It is related to the twist angle to be made (in other words, determined by the ratio of the twist rate of the thread to the pull rate of the thread). Since the strength of the nanofiber arrangement in the focusing zone (spinning triangle) is lower than the strength of the yarn, the focusing on a partially twisted yarn with a substantially circular cross section is substantially in the nanofiber forest or either. It is selectively preferred to be completed approximately 50 mm inside of that type of preliminary main assembly. Selectively and more preferably, this substantially completed focusing for producing the triangular tip of the spin occurs within about 5 mm from the nanotube forest. The optimum focusing distance also depends on the height of the forest. Optionally preferred, a substantially completed focus on a partially twisted yarn with this substantially circular cross section is less than 50 times the average height of the nanofiber forest. Occurs within the distance from. Selectively, more preferably, this substantially completed focusing occurs within a distance of less than about 5 times the average height of the nanofiber forest or any type of preliminary major assembly.

It is also important to note that the initial twist core formation in Figure 2 is clearly approximately in the center of the twisted wedge between the drawers. In some cases, thread core formation preferably appears at 1/4 to 3/4 of the distance between the end of the wedge and the apex of the wedge. In some cases, it is equally preferred that the core of the twisted fiber appears between 1/4 and 3/4 of the lateral distance between the bilateral wings of the wedge.

Surprisingly, we found that the pull-out angle (the angle between the pull-out direction and the nanofiber direction in the forest) was 90 degrees, almost 0 degrees (almost orthogonal to the plane of the substrate and the attached forest). Notice that it can change effectively between. For some spinning processes the withdrawal angle is preferably between about 90 and 60 degrees, and for other processes the withdrawal angle between about 0 and 50 degrees is preferred.

In some cases, the nanofiber forest is stripped from the growth substrate and spun into nanofiber yarns, ribbons, or sheets without being attached to the growth substrate. This stripping process can sometimes occur between spinning processes. If the forest substrate does not limit the withdrawal angle, the withdrawal angle optionally varies from 85 degrees above the forest plane to 85 degrees below the forest plane.

The nanofiber forests stripped from the growth substrate are optionally stacked on top of each other to provide a layered arrangement from which the nanofiber yarns are spun (see Example 43). Optionally, these nanofiber layers can optionally be mechanically compressed perpendicular to the plane of the forest to provide some degree of interpenetration between the nanofibers within the adjacent nanotube forest layers. Forest layers in laminated nanotube forests may optionally contain nanotubes of the same height and density inside the forest, or they may include nanotube heights and densities inside the forest, nanotubes inside individual nanotube forests. They may differ in their chemical composition or structure, or in the selective coating material or friction aid.

Nanofibers in adjacent and in contact forests can optionally be terminated with reactive groups that cause end-to-end or near-end side wall connections between individual nanofibers or nanofiber bundles in different layers. Such a binding process allows for faster spinning speeds than otherwise possible and can improve yarn properties by effectively increasing the length of the nanofibers or nanofiber bundles.

The drawing and plying spinning process is conveniently and selectively preferably carried out near ambient temperature, i.e. at normal room temperature or temperatures reached without intended heating or cooling. However, in some embodiments, the drawing and plying process may be performed above or below ambient temperature. For example, such higher or lower temperatures are optionally employed to optimize the degree of direct or indirect binding between fibers for the drawing and plying process. For example, interfiber binding aids are employed to provide self-supporting performance for nanotube forests stripped from the growth substrate in some cases. Local heating near the edges of the nanofiber forest is effectively employed to evaporate the binding aid or fluidize the binding aid, making the withdrawal and plying process most productive. Similarly, the heating process is used for reaction with gas phase additives that facilitate the drawing and plying process or improve yarn properties. This heating is induced by absorption of various means, such as visible, ultraviolet, infrared, radio, or microwave frequencies, or resistance heating (and combinations thereof) using solid-phase or vapor-phase contact heating. ) Is used. Depending on the heating or cooling process, the temperature of the nanofibers is optionally provided between -200 ° C and 2000 ° C. Selectively more preferably, this heating or cooling process is between -20 ° C and 500 ° C. For some embodiments of the invention, selectively most preferably, the initial withdrawal step and the initial twisting step for forming the twisted nanofiber yarn are carried out at 60 ° C. or less. Local heating of areas where spinning occurs, such as the edges of nanotube forests, is more effective with resistance heating, which applies a voltage between the spun yarn and the nanotube source, which results in an electric current along the nanofiber yarn. Is executed.

One of the most beneficial configurations is to pull and twist the nanofibers in the forest from the area of the furnace (CVD is used to grow the nanofibers as a forest), or the nanofiber ribbon. Alternatively, the sheet is synthesized as a forest on a surface that continuously moves to the area drawn from the nanofiber forest. Methods of growing nanofiber forests in the furnace area are possible by various methods known in the art and modifications of these methods as shown in Example 1.

In one of the selectively preferred methods, the growth substrate is either a flexible belt or attached to a moving belt. The moving belt transports the nanofiber forest from the forest growth area of the manufacturing equipment to the area where the yarn is plyed or the nanofibers or sheets are spun. Twisted and spun nanofiber yarns, nanofiber ribbons, or nanotube sheets are optionally in a continuous process, and nanofiber yarn ribbons are optionally fused and transferred to a manufacturing step where the nanofiber ribbons or sheets are laminated. Nanofiber threads, ribbons, or sheets are optionally overcoated or infiltrated with chemicals. The agent (such as a polymer) imparts ionic conductivity to enhance the bonds between nanofibers, impart electrical insulation, or use these threads, ribbons, and sheets for electrochemical device applications. Etc.) Any of various functions are supplied.

Materials suitable for both belt or drum materials and nanotube forest growth are known throughout the text. For example, Ch. Emnegger et al. Have reported that aluminum and cobalt are compatible with nanotube-growing substrates (Applied Surface Science 162-163, 452 (2000)). In addition, L. Liang et al. Described the oxidized surface application of many metals for the growth of nanotube forests, saying that the advantage of metal oxide layers is the prevention of catalytic inactivation of forest growth. It is described (US Patent Application Publication No. 20040184981A1).

Another compatible drum material is amorphous SiO₂Or crystal SiO₂It is the outer layer of (quartz), which is an effective substrate material for the growth of nanotube forests, and it has been found that at least 8 forests grow on each (X.Li et al., Nano Letters, 5). , 1997, (2005) and Y. Murakami et al., Science, 385,298 (2004)). SiO₂Is SiO on the belt₂Layer is SiO₂On the belt used for nanotube forest growth, as long as it is thin enough (usually approximately the radius of the roller to move the belt) compared to the maximum radius of curvature of the belt so that it does not break. Also suitable for layer use.

In some embodiments, the synthesis of nanotubes to produce major or preliminary major sequences, and the spinning of nanotubes, can be performed as a continuous process that employs a rotating drum. The drum is preferably at least 50 cm in diameter. The synthesis of nanofibers on one side of the drum (such as forests manufactured by the CVD method) is followed by a nanofiber-based extraction and a subsequent plying-based, false-plying-based, or liquid densification-based spinning process that rotates. Thread production or ribbon or sheet withdrawal takes place away from the drum.

As another alternative, the production of major or preliminary major nanotube sequences and spinning of nanotubes is performed, for example, in a separate device in which a substrate containing a major or preliminary major nanofiber array is wound in a roll. This winding is unwound as a separate process from the twisting process, especially the drawing and twisting spinning process.

Example 37 illustrates such a method, where a forest-spun nanotube sheet is attached to a plastic film substrate, densification and evaporation are performed on this substrate using liquid wetting, and then the nanotubes from the plastic film substrate. By pulling out the ribbon and twisting it, it is pulled out and spun into carbon nanotube yarn.

Nanofibers on the main assembly or preliminary main assembly are optionally patterned, and patterned deposits of different nanofibers are optionally employed on the same substrate, and these different nanofibers are optionally the same or different threads. Can be spun into either. Such patterned nanofiber deposits are obtained, for example, by depositing patterned nanofiber growth catalysts and can be used to determine the diameter of the twisted yarn or the width of the spun ribbon. As an embodiment of the above invention in which a moving belt or rotating drum is used, it is desirable that the patterned nanofiber deposits be strips extending and parallel to the substrate replacement direction.

A useful alternative to patterned deposition of nanotubes is that the nanotubes grow uniformly on the substrate (eg, depositing an nanotube forest on the surface of a drum or belt by CVD) and subsequent withdrawal. Laser trimming is used for patterning nanotube arrays for twisted spinning. This laser trimming Selectively preferably, the narrow lines of the removed nanotubes are made so that the nanofiber forest separates the regions that are largely unexposed to the laser beam in parallel. These lines from which the nanotubes have been removed are preferably parallel to their direction of movement as a result of drum rotation or belt movement. Laser trimming is also used to uniformly reduce the height of nanofibers in the nanofiber forest. By so trimming the nanofibers along the length of the strips of the nanofiber forest used for spinning, the yarn structure is controlled along the length of the drawn and twisted yarn. Such trimming of the nanotube height along the length of the forest strip is optionally periodic, and the resulting drawn and twisted fibers are along the length of the fiber in the structure. It fluctuates periodically. Such variations in the yarn structure along the yarn length are for achieving characteristic variations along this length, such as variations in electronic properties, or for voids between yarn compartments of larger densities. It is useful for increasing the yarn density by providing a thin yarn compartment so that it fits in the space. Yarn structures that vary along yarn length preferably result in twisted yarns, false twisted yarns, liquid densified yarns, or bonds between nanofibers that are infiltrated with agents such as organic polymers. None of the threads.

As described in more detail below, changes in the length of the nanofibers for different sections of the above yarn change the local density of the twisted yarn, and this change in local density is the electrical characteristic of one yarn division. Can be used in a directing process that selectively transforms into the electrical properties of other yarn compartments. The effect is that various electronic devices, such as diodes based on np junctions, can be manufactured along the length of the thread. Various methods are used for this selective region patterning, which takes advantage of the effects of local density changes. The local density of a particular division yarn division is such that the nanotube length affects the bonds between the fibers, thereby the distribution of twists between the different divisions of yarn, ie the yarn density (porosity) with respect to the division. It depends on the length of the nanofibers within the compartment as it affects the dependence of the local yarn density on the applied tensile strain. The electrical conductivity of the compartments, and the temperature rise caused by the current through the yarn, are also affected by the difference in porosity between the compartments and the change in the number of contacts between the fibers per nanotube.

Differences in porosity along the yarns protect one yarn division from selective doping of different yarn divisions, their selective chemical modifications, or chemical exposure effects affecting other yarn divisions (different yarns). Can be used for (by selective infiltration of protective chemicals into the compartment). These methods form the initial basis for thread lithography of device embodiments and allow the construction of electronic devices within nanofiber threads (see section 10 (a)). The difference in porosity between different yarn divisions with different structures can be adjusted by changing the tensile stress applied to the yarn. Also, as useful for this new type of yarn lithography, selective heating of different yarn divisions as a result of differences in porosity and differences in electrical conductivity of these divisions can result in selective deposition, selective reactions, Or it can be used for the selective removal of special chemicals from a particular yarn compartment.

The properties and interactions of the nanotubes being processed by various agents; the final yarn, ribbon, or sheet; or the properties of the intermediates or final products made from the yarn, ribbon, or sheet, or the final product incorporating them. Can be used to modify. These agents can be selected to optimize thread properties such as friction or bond, strength, thermal and electrical conductivity, chemical reactivity, and surface energy and chemistry, but are not limited to them.

Compatible agents provide the desired function in either the solid, liquid, or gas-absorbed state, from the gas, vapor, or liquid state, from the gas plasma, suspensions, solutions. , dispersions, emulsions or co, applicable from Lloyd, electrochemically from a solution, or particles, by infiltration of the fiber or layers, and by other methods well known to the skilled person with respect to applications of the art. These agents can be applied to preliminary major assemblies such as nanotube forests, to major assemblies, or after the formation of strands, ribbons or sheets. Agents for chemical or physical modification of the interactions between carbon nanotubes and nanotubes in the nanotube forest for the manufacturing process of threads, sheets, or ribbons are selectively preferably vapor, vapor, or It is supplied in a plasma state.

The agents used to alter the properties of the pre-major assembly, major assembly, or thread, ribbon, or sheet may be an oxidation reaction, a reduction reaction, or, for example, (1) molecular or polymer to an nanotube. Or covalently bond ionic types, (2) form non-covalent bonds such as in van der Waals and charge transfer bonds, (3) covalent or non-covalent types that can be hydrogenated. As in a functional group substitution reaction, such as covalently bonding and / or (4) physically overcoating with a polymer, metal or metal alloy, ceramic, or other material, nanotubes. It can be selected to physically or chemically modify the surface of the fiber. The agent may choose to encapsulate, coat, or coat at least partially individual nanotubes or nanoscale bundled nanotubes, regardless of binding.

Regardless of the nature of any bond, the drug is on the same order as the nanotubes: nanolayers, nanofibers, and nanoparticles, and thereby or otherwise inserted between the nanotubes and between them. It can be selected to have one or more physical dimensions to create a variety of physical or chemical interactions. Does such an interaction facilitate the detention of tubes to each other, their relative movement, and the transfer of electrical or thermal or optical or acoustic energy between them? Or limiting, or facilitating or limiting the transfer of strain or compression or shear or rotational forces between them, but is not limited thereto. Regardless of their size and nature of the interaction, they are inserted to separate the nanotubes, thereby limiting or facilitating their interaction, or occupying the gaps between the nanotubes but not inserting or Agents can be selected that do not separate them and therefore or otherwise allow or facilitate direct tube-to-tube contact.

Although the above agents can be applied to preliminary major assemblies, major assemblies, or interactions between individual or bundled nanotubes inside threads, ribbons, or sheets, by all such agents. It is also possible to facilitate or limit the interaction between the preliminary main assembly, the main assembly, or the thread, ribbon, or sheet and external effect described above. External effects include the substrates on which nanotubes are grown, the tools and equipment used to manufacture, handle, process, or store them, and the threads, fabrics, and configurations from which they are manufactured or incorporated. Examples include, but are not limited to, intermediates or final products including, but not limited to, objects. Interactions with such external effects include methods of coupling, soldering, welding, attachment, connection and intentional with external effects by other such methods used by skilled personnel in the art of connection. Connections, but not limited to. Such interactions also include, but are not limited to, intentional prevention of connections in the nature of insulating, isolating, coating, reducing sensitivity or making them incompatible.

Drugs can be selected that are applied and exist only for the intended operation and then are eliminated or deviate from performing their function in another way. Such agents can be washed away with a solvent, liquefied with thermal energy, evaporated or decomposed, decomposed or modified in either form of radiation or chemical treatment, or otherwise such. Solubility, mobility, volatility, or escape can be imparted in order for the agent to be completely or substantially removed or separated from the nanotube. Such agents are applied and exist for a particular function, but then serve no further purpose or continue to perform their initial function, or are replaced in subsequent operations and intermediates and final products. You can choose to stay with or perform additional functions. Such agents can remain completely unchanged, or can undergo chemical and / or physical changes. Examples of such agents, in their monomeric form, act as lubricants or friction modifiers for thread assemblies, followed by in-situ polymerization to enhance or facilitate adhesion and interaction of nanotubes or threads. It is a chemical substance that can be used.

Those skilled in the art will recognize that the agents described herein fulfill many functions applicable to conventional fiber processing. Recognized types include, but are not limited to, fillers, surfactants, lubricants, regulators, hygroscopic agents, binders, sizing agents, linkers, adhesives, monomers, and polymers. Those skilled in the art will appreciate that these agents are unique to or to preliminary major assemblies, major assemblies or nanotube threads, ribbons, or sheets, or to intermediates or final products made from them. You will recognize that it applies to incorporating those that introduce undiscovered or unachieved properties and features.

Preliminary major and major nanofiber assemblies and final strands may optionally be (1) nanofibers with substantially different lengths or diameters, (2) either continuous or limited in length. These include fibers of nanosize diameter, (3) nanofibers with different chemical or physical surface treatments, or (4) nanofibers with effective length of continuity. One advantage of including twisted fibers of continuity or effective continuity in twisted yarn is that these effective continuity fibers combine short length nanofibers into a mechanically robust assembly. Is to help. Optionally, most preferably, these effective continuous fibers are also either microdenier fibers (weighing less than 1 g per 9000 m length) or nanofibers. These nanofibers, which effectively have an infinite length, are preferably manufactured by electrospinning. These continuous or effective continuous fibers selectively contain large amounts of either metals or organic polymers.

One of the preferred methods for spinning single yarns containing nanofibers with different lengths, different chemical compositions, or different coatings is to effectively and simultaneously withdraw these fibers from the same preliminary or main assembly. -Twisting. This preliminary major or major assembly is selectively preferably a nanofiber forest.

It is sometimes preferred that nanofiber strands containing different fiber components for the selected application be assembled in an isolated manner, for example in a nanofiber forest, such as alternating stripping.

(b) False plying based yarn spinning from nanofiber forest We have made the surprising finding that false twisting provides a substantial portion of the mechanical strength enhancement of nanofiber plying-based spinning. Basically, false twisting is a twist in which about equal twists are applied in the opposite direction after twisting in one direction. This unexpected discovery has great practical importance for several reasons. First, false twisting is introduced very quickly, which reduces the cost of the spinning process. Second, false-twisted nanofiber yarns can be used advantageously in the formation of yarns that do not require twisting, which results in mechanical bonding between the nanofibers, and the formation and infiltration of yarns with very long nanofiber lengths. It can also be used to form threads in which the material (such as polymer) provides a mechanical bond between the nanofibers. For example, the strength enhancements found as a result of false twisting apply the high stresses required for high speed spinning, regardless of whether true twisting (net twisting in one direction) is later introduced into the yarn. to enable. Finally, the absence of significant twists on the threads of the nanotube / polymer composite enhances the toughness of the threads (the energy required to break the threads), and the presence or absence of substantial twists is otherwise excessive. This is because it interferes with the energy dissipation type process that causes large thread deformation.

Experiments in Example 40 show that the tensile strength of the yarn is significantly increased even when the twist is subsequently removed by equal twisting in the opposite direction. In this experiment, a ribbon with a fixed width was pulled from the carbon nanotube forest. In the absence of twists or false twists, the strength of the ribbon was unmeasurable. When twisted to form a twist angle of 28 degrees, the strength increased from this negligible value to 339 MPa. However, unlike yarns made of large diameter fibers, a significant percentage of this strength increase (33%) was retained when the carbon nanotubes were untwisted in an amount equal to the subsequent initial twist. Note that the increase in yarn diameter as a result of de-insertion of the twist (comparing SEM micrographs A and B in Figure 52) is relatively small.

Since strong untwisted yarns are highly desirable for use in the formation of nanotube / polymer composite yarns with both high strength and high toughness, false twisting (insertion of twists followed by deinsertion of twists) increases the strength of the yarns. This surprising finding that it can be dramatically increased is very important. This discovery provides motivation for the false twist spinning apparatus described in Figures 44-46.

In some cases, the false twisting process can be applied more than once to yarns that provide yarn densification and other desirable outcomes. Also, plying-based spinning and liquid densification-based spinning (see Section 1 (e)) are selectively beneficially applied during the spinning of nanofiber yarns.

(c) Manufacture of sheets and ribbons from nanofiber forests Although thread withdrawals from carbon nanotube forests have been described in the prior art, these threads have a maximum width report value of only 200 μm and are too weak to withstand use. We show herein that a tough sheet with any width can be pulled out of the nanotube forest.

The structural properties of the nanotube forest are important for both sheet and wide ribbon withdrawals from the nanotube forest, and the preferred structural properties of the forest are described in Section 1 (e).

FIG. 21 illustrates a drawer of a transparent nanotube sheet approximately 5 cm wide from the side wall of a multi-walled nanotube (MWNT) forest. The withdrawal was initiated by using a strip of adhesive in contact with the side wall of the MWNT forest to be torn. Importantly, the bundle nanotubes were simultaneously pulled from different heights on the side walls of the forest, so that they came together in the nanotube bundles reaching the top and bottom of the forest, thereby making them fibril. Corruption was minimized (Figs. 22 and 23). It illustrates the production speed of sheets up to 10 m / min, which is comparable to the speed commercially used for twisting wool to produce yarn. The measured surface density of the sheet is only ~ 2.7 μg / cm²Even in the case of, the length of m class is 500 cm²The seat was self-supporting during the drawer. The forest with a height of 245 μm and a length of 1 m was converted into a self-supporting MWNT sheet with a length of about 3 m. The sheet making process was very robust and there were no basic restrictions on the width and length of the sheet: for drawer speeds of about 5 m / min or less, the resulting 5 cm sheet width was the width of the forest. Was comparable to. The nanotubes are highly aligned in the withdrawal direction, as shown by the striations in the SEM micrograph of FIG.

Area density is 10 μg / cm for applications where transparency of sheets or ribbons is required²Smaller carbon nanofiber sheets or ribbons are preferred.

For twisted-based nanofiber drawers, it is preferred that the nanofibers be pulled essentially simultaneously from the full height of the side walls (ends) of the nanofiber forest.

For economic reasons, the ribbon and sheet withdrawal process is selectively performed at at least 5 m / min. Also, for economical reasons, the nanotube sheet may have a width of about 5 cm or more.

Example 22 shows that the nanotube sheet extracted in the solid state of Example 21 is a previously unknown novel and useful material state: an airgel containing highly oriented carbon nanotubes. .. Measured about 2.7 μg / cm²Due to the surface density and sheet thickness of about 18 μm, the bulk density is about 0.0015 g / cm.³Is. Therefore, the as-manufactured sheet is a transparent, strong, electrically conductive and highly anisotropic airgel. The high nanotube orientation in the nanotube sheet is illustrated by the Raman spectrum in Figure 41, which exhibits a degree of polarization of about 0.69 to 0.75. The anisotropy of light absorption (Fig. 25) also shows the high anisotropy of the nanotube sheet. Ignoring the effects of light scattering, the ratio of absorption coefficients of parallel and vertical polarized light to a single sheet as it was drawn was 4.1 at 633 nm and monotonically increased to 6.1 at 2.2 μm. The strips parallel to the extraction direction in the SEM micrograph of FIG. 22 provide more evidence for the advanced nanotube orientation of the as-extracted nanotube sheet.

For certain applications, airgel sheets and ribbons manufactured in embodiments of the invention are 0.005 g / cm.³It is selectively preferred to have a density of less than.

The width of the nanofiber sheet can optionally be increased or decreased to the width of the ribbon type. This involves adjusting the width of the side walls (or preliminary major nanofiber assemblies) of the nanotube forest that come into contact when the ribbon withdrawal begins, patterning the forest deposits, or separating the drawn wide sheet into ribbons (eg). It can be done arbitrarily (such as by cutting the base mechanically or laser-accelerated). It is selectively preferred that the width of the ribbon is at least 0.5 mm. More selectively, the width of the ribbon is 1 mm or more.

In another method of the embodiment of the invention, any width nanofiber sheet is obtained by assembling nanofiber ribbons or narrow nanofiber sheets, with adjacent ribbons or narrow sheets at least partially. It overlaps and provides a bond between the ribbons. This assembly can be performed on a flat or non-planar substrate such as a rotating drum. Since the bonds between the ribbons are usually low, binders (such as polymers such as polyvinyl alcohol) can optionally be used to enhance the bonds between the ribbons in the sheet. Instead, the bond between the ribbons is enhanced by, for example, electron beam, microwave, or other means such as using high frequency welding (possibly in the presence of a binder). Immersing the sheet in a liquid such as methanol or isopropyl alcohol and drying it (see Section 1 (d)) is another way to secure the bond (bond between ribbons and / or between ribbon and substrate). ..

(d) Liquid-based densification to reinforce nanotube sheets and ribbons Surprisingly, we found that the absorption of the liquid, followed by the evaporation of the liquid, also resulted in densification of the nanofiber sheets and ribbons by more than 300 times, and both strength and tensile strength (weight strength). Discovered that it can be used to increase.

More specifically, in Example 23, the present inventor applied these highly anisotropic airgel sheets to a thickness of 50 nm or less and a density of ~ 0.5 g / cm.³It is shown that the density can be easily increased on a highly oriented sheet having. In this special case, they simply bring the as-manufactured sheet into contact with a flat substrate (eg glass, many plastics, silicon, gold, copper, aluminum, and steel) to bring the MWNT sheet into close contact. A 360-fold increase in density is obtained by immersing the attached substrate in a liquid (eg ethanol), pulling the substrate back from the liquid and then evaporating it. Densification of the entire sheet, or selected areas within the sheet, can also be obtained by dropping or injecting such a liquid onto the areas of the sheet where densification is required and evaporating. Can be done. Surface tension acts on the MWNT sheet adjusted as described in Example 1 during ethanol evaporation to shrink the thickness of the airgel sheet to 30-50 nm. The airgel sheet can be effectively adhered to the substrate by contacting the selected region with ethanol, and the airgel sheet can be densified by evaporation. Adhesion is increased because the contact area between the nanotubes and the substrate is increased due to the drop in airgel thickness.

Example 27 shows that the densification process substantially enhances the mechanical strength of the nanotube sheet. Undensified, uniformly oriented sheet deposits are 120 and 144 MPa / (g / cm)³) Has the measured weight tensile strength. Density deposits containing identically oriented sheets are 465 MPa / (g / cm)³), Which is 175 if adjacent sheets in the deposit are orthogonally oriented to form a densified biaxial structure. MPa / (g / cm³) Decreased. The strength normalized by these densities is the strength of Mylar® and Kapton®, ~ 160MPa / (g / cm), which is used in ultra-lightweight aircraft and proposed for solar sailing vessels for space applications.³) (See High Performance Polymers 16,277 (2004), such as DE Edwards) and those of ultra-high strength steel sheets (~ 125 MPa / (g / cm)³)) And aluminum alloy (~ 250 MPa / (g / cm)³)) Is equal to or better than).

In Example 35, the nanotube sheet is a self-assembled woven fabric in which bundles of nanofibers branch and then recombine with other branches to form a network with some degree of connectivity in the lateral direction orthogonal to the withdrawal direction. Indicates to form. The SEM micrograph of FIG. 28 shows this branching and branch recombination. Fibril branching continues throughout the sheet, creating a laterally extending, essentially interconnected network of fibrils.

(e) Liquid densification-based spinning from nanotube forests We find that tough nanotube yarns are obtained from nanotube forests by using liquid-based densification, thereby avoiding the need for either twisting or false twisting. While Example 38 illustrates the process of pulling a ribbon out of the forest, we find that this process is also applicable to narrow yarns. If the yarn is used as it is pulled out of the forest without twisting, the mechanical strength of the yarn is too low to be measured using available equipment. The effect of liquid treatment (including liquid absorption and densification of filaments during liquid evaporation) is to dramatically increase strength as well as tensile strength (see Example 20). Compared to the case of the ribbon described in Example 36, the strength obtained as a result of densification with a liquid was 215 MPa.

Consideration of surface energy and liquid agglomeration energy is a liquid for densification-based nanotube spinning with liquids, as it is desirable that the absorbed liquid be properly absorbed into the sheet, ribbon, or thread of the nanotube. It will be a guideline for the selection of. Since the surface energy of nanotubes is dramatically affected by chemical derivatization and surface coatings (see Section 7), the choice of this liquid is this derivatization (eg, during forest synthesis, nanotube forest synthesis). It depends on whether post-treatment, or as a result of the reaction after the initial withdrawal of the nanotube ribbon, sheet or thread) is occurring. For most non-derivatized nanotube forests of Example 1, acetone, ethanol, methanol, isopropyl alcohol, toluene, chloroform, and chlorobenzene are good liquids for sheet, ribbon, or thread densification. Function. The functionality of liquids that do not work well for special types of nanotubes can be improved by the addition of appropriate surfactants. For example, water does not work satisfactorily for densification of nanotube sheets prepared using the method of Example 22 from the nanotube forest of Example 1. However, a surfactant / water mixture (either 0.7 wt% Triton X-100 in water or 1.2 wt% lithium dodecyl sulfate in water) is a satisfactory densification agent (see Example 23). .. Another condition for the selection of a liquid for densification is the viscosity of the liquid, which affects the speed of the ingress process of the liquid, and the ease with which this liquid evaporates during the subsequent processing process.

Any preferred degree of intrusion is the maximum value that can be achieved without an increase in the cost of the processing process, which is selectively preferably unnecessarily increased. However, sometimes it is useful to obtain threads, sheets and ribbons in which the liquid is absorbed only within the outer surface of these articles. The advantage of such partial invasion is primarily to obtain densification over the absorbed areas.

Various methods can be effectively used to achieve the ingress of liquids used for densification into nanofiber threads, ribbons, or sheets. These include, in other possibilities, condensation of vapors, immersion in liquids, and exposure of liquids to aerosols. Removal of the densified liquid is preferably by evaporation. In some cases, supercritical fluids can also be used to densify threads, sheets, or ribbons.

The liquid used for densification can optionally contain a binder, or other functionally useful agent that enhances thread properties (see Section 8), which is dissolved in the densification agent. Either it can be dispersed in it as a colloidal material. Useful types of colloidal particles include catalytic particles and nanofibers, especially single-walled carbon nanotubes, which are mostly unbunched.

Plying-based spinning, liquid densification-based spinning (see Section 1 (e)), and false twist-based spinning can be selectively beneficially used in any combination between yarn spinning. Also, liquid densification-based spinning may, in some cases, be either twisted-based spinning-and the twist is retained during and subsequent yarn processing, or subsequently partially or completely removed. Combined at the same time. In Example 38, the inventors achieved a uniform twist due to the pre-plying densification of the drawn ribbon, even when the applied twist was very low (corresponding to a 5 degree helix angle). Indicates that it is possible to obtain a single yarn. In the absence of pretreatment by densification of liquid-based yarns, the application of such low twist yarns results in uneven twists and yarn diameters.

(f) Details about nanofiber forest types useful for the production of yarns, sheets, and ribbons Most types of nanotube forests are either incompatible with spinning or produce weak yarns or ribbons. The nanotube forests used for spinning have either some entanglement in the forest or other bonds between substantially parallel nanotubes, or entanglements that occur early in the spinning process. In the forest, some degree of bundle formation, in which one nanotube meanders between different bundles, is obtained by the use of a CVD type forest growth process as described in Example 1. That degree of bundling and meandering is preferred. More specifically, the nanotubes in the forest form intermittent bundles, i.e., in small groups of nanotubes where individual nanotubes are adjacent at one point along the forest height and elsewhere along the forest height. It is preferred to undergo bundle formation, which means forming small bundles with other small groups of adjacent nanotubes.

The transition from spinnable to non-spinnable or difficult-spinning forests is caused by the smaller changes in the reaction conditions used to grow the nanotube forests. Even changes in the size and type of furnace used for spinning severely change the spinnability of the forest and the ease of withdrawal of the forest. However, anyone with the usual skills of known forest growth techniques can make small changes in growth conditions to provide useful nanotube forests for nanotube sheet, ribbon, and yarn products. Would be possible.

Spinning becomes difficult if the density of nanotubes in the forest is too low. This is illustrated in Figure 56, where SEM micrographs of the growing substrate are compared for spinnable and virtually non-spinnable forests (after removing the nanotubes). Here, the small-diameter holes on the growth substrate correspond to the growth points of MWNTs. The nanotube diameter (about 10 nm) is about the same for both these spinnable forests and virtually non-spinnable forests. However, we found that the areal density at the base of the nanotube forest was 90-200 billion nanotubes / cm for a highly spinable nanotube forest.²In comparison, 9-12 billion nanotubes / cm for low density nanotube forests that are difficult or impossible to spin.²I admitted that. Also, we found that the proportion of forest base area occupied by nanotubes was higher (7% -15%) than for highly spinnable forests, making spinning difficult or impossible. It was found to be 1.1% -2.5% of the nanotube forest.

It should be understood that these nanotube density and fractional measurements of occupied forest area are most conveniently measured using the reference plane, and the nanotube forest density differs from the reference plane value. As individual nanotubes cease to grow prematurely and new nanotube growth begins on the forest base, nanotube densities and forest area fractions increase. Optionally, at least 20% of the nanotubes initiated on the base region continue to grow substantially to the top of the forest. Optionally, more preferably at least 50% of the nanotubes initiated on the base region continue to grow substantially to the top of the forest.

Given the complexity in which the terms maximum nanotube forest density and maximum% of forest area are used, they are defined as the maximum of these parameters when measured on a plane parallel to the growth surface. Also, the adoption of non-planar growth surfaces can be useful. The terms nanotube forest density and surface fraction occupied by nanotubes in that case are defined using either a non-planar growth surface or a surface substantially parallel to the growth surface.

Based on these amazing observations, the nanotube forests used directly for thread, ribbon, or sheet extraction are at least 20 billion nanotubes / cm when the nanotube diameter is about 10 nm.²Has the highest nanofiber density of. More generally, for these and other nanotube diameters, nanotube forests, which are used directly for thread, ribbon, and sheet extraction, selectively provide the highest percentage of forest area occupied by nanotubes. It preferably has about 4% or more. Selectively and more preferably, the nanotube forests used directly for thread, ribbon, and sheet drawers are at least 20 billion nanotubes / cm when the nanotube diameter is about 10 nm.²Has a nanofiber density at the base of the forest. Also, selectively and more preferably, the nanotube forests used directly for drawing threads, ribbons, and sheets have a proportion of the forest base area occupied by nanotubes, which is about 4% or more.

If the density of nanotubes in the forest is too high, and if the interactions between the nanotubes in the forest are too great, spinning the nanotube forest will be difficult or impossible. The problem here is that the interactions within the forest are so strong that the deformation induced by the withdrawal from the orientation of the nanotubes in the forest to the orientation of the nanotubes in the threads and sheets is prevented, and mainly the mass of nanotubes is pulled out of the forest. That is.

Nanotube forests used directly for thread, ribbon, and sheet drawers have the highest proportion of forest area occupied by nanotubes, selectively preferably less than 40%. Also, the nanotubes used to selectively and more preferably directly pull out threads, ribbons, and sheets have a forest base area ratio occupied by nanotubes of about 40% or less.

The product of the number of nanotubes per unit area in the forest and the diameter of the nanotubes, as measured at the base of the forest, is selectively preferably between 0.16 and 1.6. This parameter range is particularly useful for spinning sheets, ribbons, and yarns from carbon nanotube forests.

Suitable for or as a major assembly formation, this nanofiber forest can be formed on a planar or non-planar substrate, and the nanofibers in the forest are substantially the entire surface of the substrate. It is deposited over or on only part of the surface. Also, different types of nanotubes can be present in different regions of the surface or in a mixture within the same forest region.

For convenience of yarn spinning of nanotubes and withdrawal of ribbons and sheets, the minimum radius of a bent forest substrate relative to the forest occupying area is in some cases more than 10 times the maximum forest height. Whether or not the substrate is removed prior to the ribbon or sheet drawer, the use of a curved surface substrate can facilitate the withdrawal of the non-planar ribbon and sheet. For the purpose of pulling out such ribbons and sheets, the tool used for spinning or initiating the withdrawal preferably has a matching shape, which is suitable for foresting wherever this tool starts spinning. It is well balanced with the shape of the bent substrate so that it is in contact with. (g) Details on how to start pulling out sheets, ribbons, and threads Example 46 describes a method for initiating the extraction of a sheet, ribbon, ribbon array, thread, or thread array of nanotubes from an nanotube forest using an adhesive, pin array, or a combination of adhesive and pin array. explain. Interestingly, we found that contacting the adhesive tape with either the top or side wall of the nanotube forest helps to provide mechanical contact that allows the initiation of sheet withdrawal. .. Any of the vast variety of adhesive tapes and adhesives applied to the surface is suitable, 3M's various Scotch® brand adhesive tapes and 3M's Post-it® Notes adhesives. Examples include strips. Linear contact of the adhesive strips (so that the adhesive strips are orthogonal to the pull-out direction) is particularly efficient for initiating the pull-out of a sheet with a high degree of structural perfection. The reason why this top contact method is particularly beneficial is that the nanotube forest typically has non-linear side walls, and the adhesive strips are straight (or well-spaced pins are straight). This is because its use (in an array) provides a linear contact with the forest drawers for manufacturing the sheets.

A tightly spaced pin arrangement is also effectively employed to initiate the withdrawal of the seat. In one experiment, the pinout consists of a single line of equally spaced pins. In this case, the mechanical contact required for spinning was initiated by the partial insertion of a straight pin array into the nanotube forest (see Example 46). The pin diameter was 100 microns, the pin tip was less than 1 micron, and the spacing between adjacent pin tips was less than 1 mm. Satisfactory seat drawers were achieved using pin insertions between 1/3 and 3/4 of the forest height (in the range between 200 and 300 microns).

Optionally, adjacent pins in the pin arrangement have different lengths and are inserted into the nanotube forest at different depths. Similarly, instead of using a single linear array pin, the pin array can be a two-dimensional array that extends laterally. For example, a pin array consists of two or three rows of pins perpendicular to the pull-out direction, with adjacent rows staggered in the row direction at half the distance between the pins in the row direction. It is selectively preferred that the pins in the pin arrangement are approximately equidistant from the nearest adjacent pin.

The multiple ribbon or thread withdrawal process is similarly initiated using a linear array of adhesive patches or a linear array of pins distributed within the compartment. The separation distance between the adhesive patches along the length of the linear array determines the width of the ribbon or thread. The yarn is subsequently reinforced by, for example, twist-based spinning, false twist spinning, liquid densification spinning, or a combination thereof. Mechanical separation of sheet stripping patches or pin patches in a linear arrangement during the start of withdrawal is effectively employed to avoid interference during processing of adjacent ribbons or threads, such as during the introduction of twists. ..

The use of adhesive patches (or pin patches) with different lengths along the strip direction is compounded, for example, to provide yarns of different diameters (possibly different single yarns of native plying yarns with different diameters). Can be effectively used to pull out and twist adjacent strips to manufacture. Twisting at different angles or twisting in different directions is conveniently and effectively applied to different single yarns drawn using a compartmentalized adhesive or pin strip, and these different single yarns are then optionally applied. Are twisted together into a yarn containing a freely selected number of laminates. Importantly, the use of the above method for introducing single yarns of different diameters into the plyed yarn can be employed to produce high density plyed yarns, which is of smaller diameter. This is because the plying aids in filling the interstitial space between the larger diameter plyings.

(h) Spinning of nanotube yarns from sheets or ribbons of self-supporting or substrate-supported nanotubes We have illustrated that the nanotube sheets are pulled out of the nanotube forest and separated into ribbons, which are then twisted into yarn. Similarly, we show that the ribbon drawn from the nanotube forest can then be twisted to produce yarn.

For example, according to Example 36, a 3 cm wide free-standing ribbon was folded over itself along the pull-out direction and subsequently twisted to produce a 50 μ diameter yarn.

In Example 37, a sheet of nanotubes spun from the forest was attached to a plastic film substrate, the substrate was densified using liquid infiltration and evaporation, and then the sheet ribbon of nanotubes from the plastic film substrate was pulled out. Then, by twisting the ribbon, the process of pulling out and twisting the carbon nanotube yarn is illustrated.

In Example 52, liquid densified deposits of nanotube sheets can be formed on the cellulose tissue paper, the sheets or ribbons of nanotubes are easily stripped from the cellulose substrate, and these ribbons are twisted and spun. Shows that it becomes a strong nanotube thread. According to this example, any of a variety of porous substrates such as poly (propylene) and polyethylene-based paper sheets can be used as carrier substrates for the storage and transport of rolled densified nanotube yarn sheets. It can be used as a carrier substrate when separating from a substrate as a self-standing ribbon or sheet of nanotube sheets for later applications, such as twist-based spinning of yarns, formation of layered composites, and utilization of ribbons and sheets as electrodes. ..

Polymer-impregnated nanofiber yarns are: (a) densified or non-density oriented nanofiber sheets (or unidirectional nanofiber sheets) placed on a meltable substrate film or film strip. Placed so as to take a common nanofiber orientation, (b) Occasionally occurred along the nanofiber orientation to provide a laminated ribbon of appropriate width (determined according to the desired yarn diameter). The laminate is cut or otherwise partitioned, (c) while the ribbon laminate is under tension in the orientation direction, or the meltable material adheres to the nanofiber sheet and at least partially infiltrates into it. As such, the ribbon laminate is heated while the compression perpendicular to the ribbon surface is applied, (d) optionally stretching the ribbon laminate while it is at a temperature at which the meltable material can be easily deformed. , (E) optionally, can be produced by twisting the ribbon laminate while the meltable material is at a temperature at which it can be easily deformed, and (f) cooling the meltable material to ambient temperature. The meltable substrate is preferably a meltable organic polymer, the nanofiber sheet is preferably a carbon nanotube sheet, and the carbon nanotube sheet is preferably manufactured by drawing from a carbon nanotube forest.

In another useful process, (a) densified or non-dense nanotube sheets are laminated with one or more sheets of meltable sheet material to form a laminate, (b) the laminate is oriented. The laminate is heated above the temperature at which melting occurs under directional tension or under compression orthogonal to the sheet surface, (c) Cool the laminate to ambient temperature. This process can optionally be carried out to melt between the meltable material and the nanotube sheet between heated rollers that apply lateral pressure. The product of this process can optionally be cut into ribbon-shaped threads that are infiltrated with a meltable material. The meltable material is selectively preferably an organic polymer. Microslitter and winder equipment suitable for converting continuous nanotube sheets into continuous ribbons and threads for film cutting is available from Ito Seisakusho Co., Ltd. (Japan).

(i) Processing using chemical beam radiation and heat treatment after spinning and after ribbon and sheet fabrication Spinning of the twisted yarn of Section 1 (a), the false twisted yarn of Section 1 (b), the liquid densified sheet and ribbon of Section 1 (d), and the liquid densified yarn of Section 1 (e). Various means are sometimes adopted for later processing.

These methods include thermal annealing at temperatures below 2500 ° C for multi-walled carbon nanotubes and below 1700 ° C for single-walled carbon nanotubes, or irradiation with gamma rays, electron beams, microbeams, or high frequencies, for example. Includes chemical beam exposure.

Typically, the mechanical strength is increased as a result of such treatment (probably due to adhesions between tubes to single-walled carbon nanotubes and formation of covalent bonds between tubes to both single-walled and multi-walled carbon nanotubes. ), And it will be reduced by further processing. Thermal annealing can be selectively effectively combined either simultaneously or continuously, and optionally thermal annealing can be performed by resistive heating caused by passing an electric current through the nanotube threads and sheets. The conditions required to maximize strength by such a process are strongly dependent on the type of nanotube, but can be easily determined for a particular nanotube type and assembly type by someone with conventional skill in the art. .. Information on these methods can be found, for example, PMAjayan and F.Hanhart, Nature Materials 3,135 (2004), TJImholt et al., Chem.Mater.15,3969 (2003), A.Kis et al., Nature Materials It can be found in 3,153 (2004), and US Patent Application Publication No. 2004/0222081A1 by JM Tour et al.

2. Synthesis and modification of nanofibers for the production of threads, sheets and ribbons MWNTs and SWNTs are selectively particularly preferred for use in embodiments of the invention. Laser deposition, CVD, and carbon arc discharge methods are selectively preferred methods for the production of carbon nanotubes, and these methods are known in the literature (RG Ding et al., Journal of Nanoscience and Nanotechnology 1,7 (2001). ) And J. Liu et al. MRS Bulletin 29,244 (2004)). The synthetic method results in a mixture of nanotubes, which generally have different diameters. The use of catalysts for synthesizing nanotubes that are close to monodisperse in size (and size stability at the temperatures used for synthesis) dramatically reduces polydispersity in SWNT diameters, and reduces this narrower range of nanotube diameters. The nanotubes to have are useful for embodiments of the invention. SMBachilo et al. Have adopted such a method in the Journal of the American Chemical Society. It is described in 125,11186 (2003).

The twisted SWNT yarns, nanotube sheets, and nanotube ribbons of the present invention can be made from nanotube forests as described herein for MWNT yarns. However, the adjustment of SWNT forest is different from that of MWNT forest. Alcohol CVD technology is used to successfully synthesize SWNT forests (Y. Murakami et al., Chem. Phys. Lett. 385,298 (2004)). The method of forest growth described by Science 306,1362 (2004) by K. Hata et al. Is particularly useful as it results in both SWNT and MWNT forests, and has a forest height of 2.5. Can be higher than mm. In this method, catalytic activity is enhanced by a precisely controlled amount of water vapor during CVD growth of the nanotube forest.

For MWNT forests, not all SWNT forests can be used advantageously for spinning yarns and for making yarns and ribbons by forest-based processes. For this reason, SWNT forests preferably have the properties described in Section 1 (f).

Multiple forest layers can easily grow on top of each other (eg, using the method described in Nano Letters 5, 1998 (2005) by X.Li et al.), And these different layers (forest spinning, (Or when optimized for sheet or ribbon drawers) are available at the same time, thereby optimizing the processing of the material. These deposited forests can optionally be stripped from the substrate prior to the production of sheets, ribbons, or yarns according to the methods of the invention.

The nanofibers used for spinning and for the production of ribbons and sheets optionally contain coils (FIG. 14), or crimped nanofibers (FIG. 15). One advantage of such inclusions is the increased extensibility of the nanofiber yarn as a result of the increased effective fracture strain of the coiled or crimped nanofibers. One selectively preferred method for spinning such coiled or crimped nanofibers into yarn is to utilize a draw-plying assembly from the forest containing such coiled or crimped nanofibers. is there. As a catalyst, an alloy of indium tin oxide and iron is used to grow coiled or crimped nanofibers as a forest (M. Zhang et al., Jpn.J. Appl. Phys. 39,1242 (2000)).

Various methods of separating SWNTs according to their electrical properties are useful for embodiments of the invention, such as for increasing the ultimate electrical conductivity. Well-known examples for such separation are (1) the use of charge transfer agents that most easily complex with metallic nanotubes, (2) complexing with selected DNA, and (3) dielectric verses. Includes dynamics (R. Krupke et al., Nano Letters 3,1019 (2003) and RC Addon et al., MRS Bulletin 29,252-259 (2004)).

Thread function is also optimized by filling the components of nanotubes or nanotube scrolls (spiraled single-walled graphite sheets) with materials that enhance mechanical, optical, electromagnetic, or electrical properties. To. Various methods are particularly useful for embodiments of the invention for packing or partial packing of nanotubes. These methods for SWNTs and MWNTs typically include the first step of opening the ends of the nanotubes, which use vapor phase oxidants, other oxidants (such as oxidizing acids), or mechanical cutting. Can be conveniently executed. Open nanotubes (as well as scroll nanotubes) can be filled into nanotubes in a variety of ways, including the transport of vapors, liquid phases, melt phases, or supercritical phases. Carbon nanotubes, KCl and UCl₄Mixtures of; KI; Mixtures of AgCl with either AgBr or Agl; CdCl₂CdI₂ThCl₄LnCl₃ZrCl₃ZrCl₄, MoCl₃FeCl₃; And Sb₂O₃In the prior art for filling with, a method of filling the nanotubes with metal oxides, metal halides, and related materials such as these can be used. In any additional steps, the nanotubes filled (or partially filled) with them may optionally reduce the material inside the nanotubes, such as, for example, Ru, Bi, Au, Pt, Pd, and Ag. It can be processed to perform conversions such as thermal decomposition of metal salts to produce metals. M. Monthioux provides useful insights into these methods for packing and partial filling of nanotubes, including filling the nanotubes during nanotube synthesis (Carbon 40, 1809-1823 (2003)). Partial or complete filling of various other materials useful for embodiments of the invention is described in J. Sloan et al., J. Materials Chemistry 7,1089-1095 (1997)).

Nanofibers need to be carbon-free to serve the embodiments of the invention, and many processes are well known in the art for producing non-carbon based nanofibers. Here are some examples: Superconducting MgB from the reaction of single crystal B nanowires with the vapor of Mg₂Growth of nanowires (Y.Wu et al., Advanced Materials 13,1487 (2001)), Growth of superconducting lead nanowires by thermal decomposition of lead acetate in ethylene glycol (Y.Wu et al., Nano Letters 3,1163-1166) (2003)), Solution phase growth of selenium nanowires from colloidal particles (B.Gates et al., J.Am.Chem.Soc.122,12582-12583 (2000) and T.Mayer et al., Chemistry of Materials 15, 3852 -3858 (2003)), and the synthesis of lead nanowires by mold induction on steps inside channels within porous membranes or on silicon substrates. The latter method and various other methods of producing metallic and semiconducting nanowires of the appropriate type for carrying out embodiments of the invention are described in Nano Letters, such as Wu et al. 3,1163-1166 (2003), and detailed in the accompanying references. Y.Li et al. (J.Am.Chem.Soc.123,9904-9905 (2001)) showed a method for producing bismuth nanotubes. Also, X. Duan and CM Lieber (Advanced Materials) 12,298-302 (2000)) showed that laser-assisted catalytic growth can be used to produce large amounts of high-purity semiconductor nanofibers. These nanofibers obtained are particularly useful in embodiments of the invention, as well as single crystal nanofibers (GaAs, GaP, InAs and InP) in the binary group of IIIV elements, ternary III-V materials (GaAs / P). , InAs / P), binary II-VI compounds (ZnS, ZnSe, CdS, and CdSe), and binary SiGe alloys. Si nanofibers, and doped Si nanofibers, are also useful in embodiments of the invention. The adjustment of Si nanofibers by laser ablation is described by B.Li et al. (Phys. Rev. B59, 1645-1648 (1999)). Various methods for producing nanotubes of numerous useful materials are described by R. Tenne in Angew. Chem. Int. Ed. 42, 5124-5132 (2003)). In addition, GaN nanotubes can be effectively produced by epitaxially growing a thin GaN layer on ZnO nanowires followed by removal of ZnO (see Nature 422,599-602 (2003) by J. Goldberger et al.). MoS commercially available from Mo6 (Teslova 30,1000 Ljubljana, Slovenia)_9-xI_xNanofibers with an approximate composition of are included in the preferred composition (most specifically for x between about 4.5 and 6).

Some of these non-carbon based nanofibers, in some cases, do not have favorable dimensional properties for the fabrication of nanofiber spinning and nanofiber sheets and ribbons, but are optionally within the preferred dimensional range by prior art. How to synthesize nanofibers of the type is taught. For example, the synthesis of nanofibers in an anodized alumina template is a well-known technique, where nanofiber diameter and nanofiber length are appropriate for the thickness of the anodized alumina and the diameter of the channels within the anodized alumina. It can be adjusted appropriately by various choices.

Nanoscrolls are particularly useful in embodiments of the invention. We have found that nanoscrolls provide better mechanical properties than multi-walled nanotubes and other non-scrolling nanofiber types. These nanoscrolls are thin deposits of individual sheets or layered material sheets that are automatically wound to produce scrolls and are structurally similar to jelly rolls. Most sheet-shaped materials-as long as the lateral sheet dimensions are large enough and the energy gain from the non-covalent bond between the layers of the scroll can compensate for the elastic energy costs that form the scroll-self-organize into the scroll. it can. Some examples of materials that have been shown to form nanoscrolls are bismuth, BN, C, V.₂O₅, H₂TYi₃O₇, Gallium hydroxide oxide, oxides of zinc and titanium, CdSe, Cu (OH)₂, Selected perovskite, InGa / GaAs and Ge_xSi_1-x/ Si heterolayer structure, and MTS₃And MT₂S₅Mixed layer compounds, such as (M = Sn, Pb, Bi, etc .; T = Nb, Ta, etc.). The generality of the scrolling process for layered materials, from bismuth to carbon and boron nitride, means that there are numerous candidate materials to choose from for yarn formation. The threads of the present invention are also manufactured at low cost, as scrolls are easily manufactured from stripping materials that are currently manufactured in large quantities at low cost. Methods for synthesizing nanoscrolls from a large number of layered materials are known and these methods can be used to carry out embodiments of the present invention (LMViculis, LM, JJMack, and RBKaner, Science 299,1361-1361 (2003)). ZLWang, Advanced Materials 15,432-436 (2003); XDWang et al., Advanced Materials 14,1732- (2002); WLHughes and ZLWang et al., Applied Physics Letters 82,2886-2888 (2003); JWLiu et al., Journal of Physical Chemistry B107,6329-6332 (2003); and YBLi, Y.Bando, and D.Golberg, Chemical Physics Letters 375,102-105 (2003)).

3. Non-forest nanofiber assembly suitable for making threads, sheets and ribbons A variety of other nanofiber arrays can be employed as an alternative to adopting nanotube forests as preliminary or major assemblies.

For example, Example 37 describes a method of twisting and spinning carbon nanotube yarns from a densified nanotube sheet. In this example, the densified nanotube sheet serves as a preliminary main assembly. A free-standing MWNT sheet (manufactured as in Example 21), which remains in the drawer, was placed on a substrate (eg, glass, plastic, or metal foil) and densified using a liquid. .. Plastic substrates such as Mylar film were most conveniently used. The densified sheet of the desired width was easily withdrawn from the substrate using adhesive tape to initiate the extraction process (where the nanofiber threads of the ribbon are made by stripping the nanotubes from the substrate). One end of a strip of separated sheets was attached to the motor to introduce twisting while the yarn was pulled out, resulting in a yarn of uniform diameter.

Example 36 illustrates that a MWNT sheet manufactured in a solid state is conveniently drawn out and spun into a large diameter yarn having a uniform diameter. In this example, the densified nanotube sheet acts as the main sequence. An as-extracted nanotube sheet 10.5 cm long and 3 cm wide was folded on its own to produce a pseudo-circular assembly with approximately the same length. One end was attached to the tip of the spindle and the other end was attached to a fixed copper wire. With the introduction of twisting, uniform spun yarn was formed at a twisting level of ~ 2000 times / m.

Airgels containing sufficiently long carbon nanotubes are suitable for twist-based spinning of yarns, but the benefits of lateral stress transfer are realized unless the ratio of nanofiber length to nanofiber circumference is 5 or more, more preferably 20 or more. Not done. Nanotube yarns were previously spun at about 100 ° C in a CVD furnace and then twisted either simultaneously or subsequently, but according to the experiments described, the ratio of nanofiber length to yarn circumference is Less than a unit, which is insufficient to realize the benefits of lateral stress transfer generated by twisting. (Y.Li et al., Science 304,276 (2004), IAKinlock et al., International Publication No. WO2005 / 007926A2, and M.Motta, Nano Letters 5,1529 (2005)) Carbon nanotube aerogels consisting of nanotubes of appropriate length are densified based on false twist based yarn spinning and liquid densification based yarn spinning, and aerogel ribbon or sheet liquid drawn from the aerogel. Can be used as a preliminary main arrangement for the production of durable ribbons and sheets. The drawn ribbons of these airgels, optionally reinforced by liquid densification, can be converted to nanotube yarns using twisting, false twisting, or a combination of false twisting and twisting.

Other nanofiber airgels also include false twist-based yarn spinning and liquid densification-based yarn spinning, as well as durable ribbons and liquid-based densification-based reinforcement of the airgel ribbon or sheet drawn from the airgel. Suitable as a preliminary main sequence for the manufacture of sheets. The drawn ribbons of these airgels, optionally reinforced by liquid densification, can be converted to nanotube yarns using twisting, false twisting, or a combination of false twisting and twisting. Examples of nanofiber gels that provide useful compositions for spinning and sheet and ribbon formation are vanadium oxide airgels, vanadium oxide / carbon nanotube composite airgels, and nanofibril cellulose airgels. Preparations for these types of gels were made by JS Sakamato and B. Dunn (Journal of the Electrochemical Society 149, A26 (2002), W. Dong et al. (Science and Technology of Advanced Materials). 4,3 (2003)) and by H. Jin et al. (Colloids and Surfaces A 240,63 (2004)). Well-known methods for increasing nanofiber length and minimizing length-to-width ratios have been successfully adopted to improve the spinnability of the fibers and the adaptability of these nanofibers to sheet and ribbon pullability. , Or obtained.

A magnetically oriented nanofiber sheet, an electrically oriented nanofiber sheet, or a shear flow oriented nanofiber sheet can be adopted as the main arrangement of yarn spinning. These nanotube sheets can be obtained with a variety of processes, such as the application of shear flow fields, magnetic fields or electric fields during the filtration process of feeding the nanotube sheets (MJ Casavant et al., J. Applied Physics 93). , 2153-2156 (2003)), such embodiments are useful in carrying out embodiments of the invention.

In some cases, for the purpose of removing impurities, some applications may be introduced, for example, in surfactants that may be used for suspending nanotubes and functional groups that may be introduced during nanotube purification. It is useful to thermally anneal the nanofiber sheet to remove such impurities. Selective annealing of the carbon nanotubes is preferably performed at at least 400 ° C. for 0.5 hours or longer. To retain the structure of the carbon nanotubes, annealing is selectively performed in an inert atmosphere, preferably at temperatures below about 1500 ° C for single-walled nanotubes.

Such an oriented arrangement of nanofibers can be employed as the main assembly for twist-based spinning. The present inventors have found that such twist-based spinning is less successful in producing high-strength yarns if the following conditions are not met: The condition is that for a twisted yarn of diameter D, the maximum total number of twists in one direction per fiber length is at least about 0.06 / D turns, and an important component of nanofibers is (i). Maximum width Has a value of less than about 500 nm, (ii) a minimum width-to-length-to-width ratio of at least about 100, and (iii) a ratio of nanofiber length to yarn circumference greater than about 5.

We found that the oriented carbon nanotube sheets described in the literature (having nanofiber lengths less than a few μ) are largely unsuitable for producing high-strength twisted yarns with a diameter of 1 μm or more. I found. The reason found by the present inventor is that the nanofiber length is preferably at least 5 times the thread circumference, and more preferably 20 times the thread circumference. However, we have adapted the filtration-based sheet forming process to longer nanotubes (eg, nanotube products up to 300 μ length in the method of Example 1), and such longer nanotubes are the practice of the invention. It has been found that it is selectively and preferably adopted as a form.

Yarns produced by the coagulation spinning process are also preferably useful in embodiments of the present invention as long as the length of these yarns is increased to at least 5 times the circumference of the yarn. This condition has not been realized for spun yarns in the literature. Further, the nanotube length of these yarns is more preferably at least 20 times or more the circumference of the yarn. These coagulation-based spinning methods include, for example, coagulation spinning using a polymer such as polyvinyl alcohol in a coagulation bath (B. Vigolo et al., Science 290,1331 (2000); RH Baughman, Science 290,1310 (2000). B. Vigolo et al., Applied Physics Letters 81,1210 (2002); and AB Dalton et al. Nature 423,703 (2003)), coagulation spinning with aqueous nanotube dispersions and acidic or basic non-polymeric coagulants (simultaneous pending application PCT Patent Application No. US2005 / 035220), and acidic spinning solutions and non-polymers. A spinning process using a polymeric coagulation bath (VADavis et al., US Patent Application Publication No. 200303170166) can be mentioned. However, for the spinning process of spinning solutions in which polymer coagulants are used or contain polymers, we have brought the polymer-containing yarns to a preferably highly oriented state during the presence of the polymer. It has then been found that it is most preferable that the polymer be substantially removed (eg, such as pyrolysis) prior to the twisting process. In the embodiments of the invention of this section, the yarn formed by cohesive spinning can be the main assembly of the spinning process. We have determined that a highly oriented hollow nanofiber yarn comprises a twisting process if the length of the shortest nanofiber yarn in the hollow yarn is greater than about 5 times the yarn circumference. It was also found that it is suitable for the practice of.

Nanotube yarns spun from superacids (VA Davis et al., US Patent Application Publication No. 200301170166; W. Zhou et al., J. Applied Physics 95, 649-655 (2004)) are also embodiments of the invention for the adjustment of twisted yarns. Especially preferred as the main assembly in some cases. However, the nanofibers in the yarn spun in the prior art using the superacid spinning process are too short to derive high performance carbon nanotube yarns with micron and larger diameters without the adoption of polymer binders. The reported thread diameter is about 60 μm or more (W. Zhou et al., J. Applied Physics). 95,649-655 (2004)). Therefore, due to both large yarn diameters and short nanotube lengths, twist insertion does not improve the performance of these yarns either as they are spun or after thermal annealing. According to the teachings of embodiments of the present invention, twisting or drawing / twisting is preferably a nanofiber length relative to the yarn circumference, which is greater than about 5 for the key components of the nanofiber tube in the yarn. Brings the ratio of. More preferably, the important component of the nanofibers in the yarn has a minimum ratio of nanofiber length to yarn circumference, greater than about 20. Optionally, most preferably, the major components of the nanofibers have a ratio of nanofiber length to thread circumference greater than about 20. Therefore, the prior art acid spinning yarn having a yarn diameter of 60 μm can be twisted if the length of the nanofiber yarn is about 940 μm, and the advantage of twisting can be substantially obtained, and the spinning in the super acid of the prior art can be obtained. It is about 1000 times the possible nanofiber length of the fiber.

4. Twisted and false twisted polymer-free nanofiber yarns with diameters not previously available Embodiments of the present invention provide a twisted yarn having a diameter 1000 times or smaller than that of the prior art twisted yarn. Approximately 100,000 individual carbon nanofibers are cross sections of nanotube yarns with a diameter of 5 μm, nanofibers of 5000 nanofibers per square μ, compared to 40-100 fibers in cross sections of typical commercial wool and cotton yarns. Corresponds to fiber density. By comparison, the minimum diameter of the nanotube fibers reported using the prior art is more than 10 times larger in diameter than the micron diameter twisted carbon nanotube yarn described in Example 2. Since the yarn volume and linear density per 1 m of yarn length are proportional to the square of the fiber diameter, the yarn of the embodiment of the present invention is based on the values obtained with the textile yarn of the prior art in terms of linear density and volume per meter. Is also 100 times lower. Microfibers are extremely soft to the touch, drapeable, and widely used due to their high absorbency, and are widely used in the textile industry for less than 1 denier (ie, 1). It is defined as (less than or equal to den), that is, the weight of one filament is less than 1 g per 9000 m, or 0.11 mg / m. By comparison, the linear density of non-twisted MENT yarns with a diameter of 5 microns (commonly known as "single, single yarns" containing about 100,000 fibers in cross-sectional area) is typically about 10 μg / m (0.09 den). It is compared with 10 mg / m (90 den) for normal cotton yarn and 20-100 mg / m (180-900 den) for yarn.

As a result of the smaller diameter of the nanofiber strands and the component nanofibers, 10 more than traditional microfiber strands.²And 10⁶A small linear density is obtained by the coefficient of, which makes the yarn promising for textile applications in military garments and spacesuits. Advantages in textiles include a combination of "breathability" and water and wind resistance, impermeable to bacteria such as charcoal fungi of high density micron diameter threads, high thermal conductivity and high electrical conductivity, radio frequency and microwave. Wave absorption, protection against electrostatic discharge, protection against intrusion, unpleasant hardness of some electronic fabrics and outstanding control fabric softness and drapeability. Toughness comparable to Kevlar fibers used in bulletproof vests, resistance to knot and friction-induced breakage, high breakage strain, and high stability to UV and heat are other major advantages of nanotube yarns for textile applications.

As a result of these gains, for some application areas, the yarns of the selectively preferred embodiments of these low denier applications are nanofiber single yarns with a diameter of less than about 10 microns and 1 m. It has the above thread length. For these applications, optionally, more preferably nanofiber single yarns with a diameter of less than 5 microns. Optionally, the drawn and twisted yarn contains at least 500 nanofibers that penetrate each 1 square micron of yarn cross-sectional area. Selectively, more preferably, at least 1000 nanofibers penetrate each 1 square micron of the cross-sectional area of the nanofiber yarn.

5. Development of methods for inserting twists during spinning, densifying, and storing filaments Various known methods of twist insertion can be used to introduce twist during spinning the nanotubes into the yarn. Such methods include, but are not limited to, ring spinning, mule spinning, cap spinning, open-ended spinning, vortex spinning, and false twist spinning techniques (E.Oxtoby, Spun Yarn Technology). , Butterworths, 1987 and CA Lawrence, Fundamentals of Spun Yarn Technology, CRC Press, 2002). Mule spinning has the disadvantage of being a batch process (spinning and then winding), but has the advantage of not requiring a ring or traveler.

A new continuous spinning device is provided for spinning fine and ultrafine nanofibers, whereby twisting is introduced while winding the spun yarn onto a bobbin. The device is schematically shown in FIG. The fiber source is the nanotube forest (3801) on the substrate. The produced thread (3802) is allowed to pass through an early thread guide (3803). The spinning device is in contact with a spindle base (3805), a donut-shaped winding disc (3806) with a winding yarn guide (3804), an electromagnet (3807), and a ferromagnetic spindle base, typically made of steel. Includes donut-shaped metal magnetic disk (3808). At one end, the spindle is driven by a variable speed motor (not shown). At the opposite end is a removable bobbin (3811) that picks up and stores the spun fiber. The spindle base is provided with a spindle pin (3810) protruding from the spindle base, which passes through the center of the magnetic disk (3808) and the ferromagnetic winding disk (3806). The variable speed motor makes the spindle angular velocity ω₁The winding disk is rotated by magnetically induced friction between the spindle base (3809) and the magnetic disk (3808), and between the magnetic disk and the ferromagnetic winding disk (3806). An electromagnet is used to introduce a variable braking force on the winding disc, thereby resulting in an angular velocity with respect to the spindle (ω).₂) Is reduced. Rotation of the drawn nanofibers around the spindle axis introduces twisting, which causes the spun yarn to be wound onto the spindle by a slower rotation of the winding disc, thereby forming the yarn. Winding speed is ω₁And ω₂Velocity difference between [ω (winding) = ω_1-ω₂], Which can be adjusted continuously by changing the voltage applied to the electromagnet. Advantageously, both the twist level and the spinning speed can be controlled independently by an electronic interface that independently adjusts the motor speed and the applied magnetic field. With this system, the minimum tension is applied to the spun yarn and the spinning of the yarn can be handled with both high and low braking forces. This same system can also be used to stack a large number of single-strand yarns together to continuously produce multi-strand yarns. In that case, the nanotube forest is replaced by a reel of unlapped yarn.

Various modifications of the spinning apparatus can be effectively adopted. For example, the magnetic disk (3808) is removed, and a direct frictional force between the winding disk and the spindle base is provided by a spring that loads the winding disk. If the spring load is applied by an electrically controlled actuator (such as a ferroelectric or ferroelectric actuator), the electromagnet (3807) is removed. As an alternative, the magnetic disk (3807) replaces the indirect mechanical coupling between the winding disk and the spindle base with an electrically controlled thickness ferroelectric disk. In the latter case, the electromagnet (3807) can be removed and the frictional force between the spindle base, the ferroelectric disc, and the winding disc can be created by a spring load.

Another preferred method of spinning carbon nanotubes into yarn is to employ a direct spinning method in which the spun yarn is wound onto a bobbin and twisted. The device is outlined graphically in Figures 19 and 20.

FIG. 19 consists of a substrate pedestal (1901) located on a bobbin (1902) that rotates simultaneously around a take-up shaft (1904) and around a shaft (1903) that coincides with the thread shaft. Spinning unit (1900) is shown. Rotation around the yarn shaft introduced a twist (1905) into the extracted nanotube assembly (1906), which spun on a bobbin firmly mounted on the drive roller by rotation around its own shaft. The thread is formed while the thread is wound up.

FIG. 20 is given the details of the board cradle and includes six board units (2001) supported by a network of board holder arms (2002), a central shaft (2003), and a cross support (2004). Shown. However, it can be seen that many design changes are possible that are consistent with the abbreviated scheme. Similarly, MWNT forests can be grown from one or both sides of the substrate (2005). The advantage of growing nanotubes from both sides is that it increases the capacity of the spinning machine.

The advantage of this direct spinning method is that the alignment between the spinning and the yarn axis eliminates the expansion due to spinning, the nanotube yarn does not contact any surface until the twist is inserted, and the cohesion that is fully provided by then. It can be handled without damage by force. The twist level can be set independently while winding by using a variable speed motor to move the take-up and the drive of the plying independently of each other.

The equipment of FIGS. 19 and 20 uses a substrate in a flexible belt, an nanotube forest, to bend away from the threads produced by nanotube extraction and continuously move to a furnace for nanotube growth, and then It can be made continuous by returning to the point of nanotube extraction for making threads.

Techniques known in the art such as tension monitoring in yarn, automatic loading of new substrates and removal of used substrates, automatic threading and lifting, and systems for construction management of yarn packages Can be attached to spinning machines to improve functionality and productivity.

Surprisingly, we have found that deformation or brake spinning of open-end spinning can be downsized by a factor of more than 1000, from applicability to micron-diameter fibers to nanometer-diameter. Open-end spinning of conventional textile fibers involves the following steps: (1) Adjusting the assembly of linear, parallel and individualized fibers; (2) How to remove the single fiber from the assembly; (3) Cup shape Means for transferring fibers to the inner surface of the collector (rotating body); (4) Means for supporting and driving the collector at high speed; (5) Means for collecting fibers from the collector, in which twists are inserted and yarns are inserted. And wind the thread into the package. All of these steps are required for open-end spinning of nanofibers, but we have found that modifications are needed for nanoscale fibers to operate the process well. That is, (1) ensuring that the nanofibers are selected so that they do not adhere to the surface on all surfaces that the nanofibers come into contact with and on the surface of the nanotubes, and (2) collectors for personalization and twist insertion. To develop and use nanoscale-applicable methods for nanofiber supply, which are properly oriented for supply to. Unlike in normal spinning, properly individualized nanofibers contain thousands of nanofiber components that must be suitably assembled during the spinning steps of the yarn or during the pre-processing of the yarn. It may be a bundle or a robe. Natural fibers, on the other hand, also contain nanofiber components, but are self-organized by the natural ecology.

A blueprint for open-end spinning suitable for nanofiber spinning is shown in Figure 43. Explanatory diagrams show that the nanotubes are pulled away from the nanotube feed package (4301) deposited by sheet withdrawal from the preliminary arrangement. The roller (4301) can be long enough to maximize storage. The nanofibers and nanofiber assemblies are separated from the feed rollers by a high speed beater (4302) installed in close proximity to the feed rollers, with a large number of highly surface-finished fine pins. The nanofibers and nanofiber assemblies are discharged into a transport tube (4303), where the airflow carries the nanofibers to the rotor (4304). The air flow is generated by keeping the air pressure in the rotor below atmospheric pressure. The nanofibers and nanofiber assemblies gather on the inner surface of the rotor and, under the influence of centrifugal force, slide into the groove (4305), where they form a generally parallel fiber assembly. Once a sufficient number of nanofibers have accumulated in the groove, seed yarn (4306) is introduced into the rotor with the help of low pressure, where the nanofibers introduce a twist that is introduced once per rotation of the rotor. Start and form a thread. Immediately the yarn is recovered by a roller (4307), but in the yarn formed in the rotor for the purpose of increasing the twist of the tail (4306) and improving the reliability of the spinning, similar to normal open-end spinning. A doffing tube navel (4308) is used to insert the false twist into the. As the yarn is formed, it is wound by the package winder (4310) onto the yarn package (4309). Changes in the basic design that will be apparent to those skilled in the art are possible.

False twist spinning is a conventional textile process used to impart bulkiness to staple fibers where a second yarn is available to trap the false twist in a continuous filament or twin yarn structure. False twist spinning has been limited to use with ordinary staple fiber yarns. This is because once the yarn has passed through the twister, the twist disappears and its strength and tensile strength are lost. Surprisingly, we find that the nanofiber yarns described herein retain strength and tensile strength after the introduced twists have been removed. That is somewhat similar to the case of densifying the yarn. This means that false twists can be used to produce yarns suitable for use with or without the application of binders between the yarns, such as infiltrated polymers. This discovery provides motivation for the false twist spinning apparatus described in Figures 44-46. Even if the nanofiber yarn is later subjected to a permanent twist introduction, the introduced false twist increases the strength of the nanofibers, resulting in higher processing speeds without causing yarn breakage. is there.

These measurements on the effects of twist insertion and equivalent twist deinsertion (referred to as false twist insertion) are provided in Example 40. The strength obtained (if equal twist deinsertion continues after twist insertion) (113Mpa) is much higher than the negligible strength of the untwisted yarn, but the degree of initially inserted twist insertion is Lower than when retained (339 MPa). Nevertheless, yarns that have undergone a twist insertion / detwisting process are highly desired for yarn applications in the formation of nanotube / polymer composites, have high strength and toughness, and are also between very long nanotubes. It is also strongly desired to develop high-density packing that transfers stress as a result of van der Waals interaction. What is important here is that the preferably laterally bonded nanofiber yarn has the highest strength at zero twist. Twisting is introduced to provide a lateral bond. However, infiltration of nanofiber threads with a coupling agent (eg, infiltration polymer) also provides the required lateral bond. In addition, if the nanotubes are reasonably long, high strength is provided by any false twist that provides a high density of yarn (and a moderate enhancement of the binding relationship between the corresponding nanofibers).

Corresponding to these discoveries, embodiments of the invention are provided in which false twists are introduced and later infiltrated with a binder such as a polymer. The variety of binders is wide-ranging, including polymers, metals (eg melt infiltration, chemical or electrochemical infiltration), and other organic and inorganic materials (SiO).₂Etc.). Binders such as polyacrylonitrile are optionally pyrolyzed, and additional infiltration steps can be followed by additional pyrolysis steps to obtain optimal filling of the nanofiber yarn with the binder.

Similarly, false twist spinning can be used as a pretreatment for inserting low levels of actual twist to easily provide a high twist area where the yarn can be densified at high speed. If there is no preliminary densification, the intended production rate will be reduced and higher levels of actual twisting will be required. A device for doing this is shown in Figure 46, where a preliminary main sequence (4601) is drawn from the substrate and twisted by a false-twisted spinneret 4602, resulting in a highly twisted yarn 4603 upstream of the spinneret. Is shown to give. The downstream division of the spinneret is the normal spinning system 4604, which consists of a bobbin (4605) for winding the yarn, a traveler-shaped hook (4606) and a drive (4607) for inserting the twist, and a false twist zone. A lower level of twist is introduced than in. The operation for giving the package construction has not been shown, but it is familiar to those skilled in the art. Since the yarn is densified by a high degree of twisting that imparts some strength, a low level of actual twist is required to achieve the proper strength for the nanofiber yarn.

The design of a false twisting system suitable for spinning nanofibers is shown in Figure 44. Nanofibers are drawn from an nanotube forest (4401) supported on a substrate (4402) and at the same time twisted by a false-twisted spindle 4403 (spinning cap) to spin triangles (4404) and highly twisted yarns (4405). ) Is formed. The yarn that leaves the spinneret when the spinning system reaches equilibrium has no twist (4406), but has some strength due to the densification provided as a result of the twisting of the upstream sector of the spinneret. The yarn is wound onto the package (4407) by the package winder (4408).

The spinneret (4403) is shown in detail by FIG. 45. The spinneret 4501 includes a cylindrical tube (4502), a compartment 4503 for placing support bearings, and a pulley (4504) for driving the spinneret at high speeds. Two toroidal ceramic yarn guides (4505 and 4506) are mounted on the opposite end of the cylinder 4502 to the pulley to support the yarn as it passes through the spinneret. A hole (4507) with a suitable cross-sectional shape is drilled through the cylinder 4502 at right angles to the shaft. Ceramic pin 4508 provides an ambient environment in which the thread can loop so that a crank for inserting the twist is effectively provided. The pin is shaped to give the thread on the axis a positive position, and a "U" saddle shape is commonly used in the plane containing the axis of the spinneret. An additional improvement is to place a narrow constriction over the pins that are placed on the spinner shaft. The pin is open at one end to facilitate threading of the spinneret.

Another method of continuously spinning carbon nanotubes and other nanofibers into yarn is to employ a direct spinning method in which the spun yarn is twisted as it is wound around the bobbin. The device is illustrated graphically in FIG. The fiber source is an nanotube forest on the substrate (10601), and other nanofiber sources can be used. The produced yarn (10602) passes through the initial yarn guide (10603). Spinning devices include a spindle (10605), a winding disc (10606) with a corresponding yarn guide (10604), a spinning motor (10607), and a winding motor (10608) that drives the winding disc through a belt (10609). At one end the spindle (10605) is driven by a variable speed motor (10607); at the other end there is a removable bobbin (10611) that winds and stores the spun yarn. The spindle (10605) is attached to the motor (10607) and the spindle pin (10610) passes through the center of the winding disc (10606). Variable speed motor (10607) makes the spindle angular velocity ω₁The winding motor (10608) rotates the winding disc at an angular velocity of ω.₂Rotate with. Rotation around the spindle axis of the drawn nanofiber assembly introduces the twist, which forms the yarn, while the faster rotation of the winding disc winds the spun yarn onto the bobbin. Winding speed is ω₁And ω₂Determined by the speed difference between [ω (winding) = ω₁-ω₂], It can be adjusted continuously by changing the speed difference between the two motors. Advantageously, both the twist level and the spinning speed can be controlled independently by an electronic interface that independently adjusts the motor speed. This same device can also be used to superimpose a large number of single-strand yarns together to continuously produce multi-strand yarns. In that case, the nanotube forest is replaced by a reel of unlapped yarn or yarn with a lower than desired superposition in the product. Although not shown, the spinning apparatus of FIG. 106 can be equipped with additional equipment to move the bobbin back and forth to collect the yarn.

We use these enhancements in the machining steps as the incredible strength enhancements of yarns, sheets, and ribbons are obtained as a result of liquid infiltration and subsequent evaporation. Example 38 shows a dramatic increase in yarn strength resulting from the infiltration of a suitable volatile liquid into the yarn followed by evaporation of this liquid. Tensile strength also increases. These effects are clearly due to the densification of the yarn due to the evaporation of the volatile liquid. If no twist was applied and the yarn was used as it was pulled out of the forest, the mechanical strength of the yarn was too low to be measured using our equipment.

The most suitable liquids for such densification and improvement of mechanical strength and tensile strength are those having a viscosity low enough to penetrate into nanofiber threads, sheets or ribbons and the ability to wet nanotubes. Is. Although the liquid used in Example 38 is ethanol, a class of volatile liquids with low viscosities and a cohesive energy density roughly commensurate with the nanofibers are also useful.

There are many systems for woven or sheet processing for adding liquids to yarns, such as spraying, padding and vapor phase surface treatment. All of these techniques can be used during spinning or sheet making to obtain increased strength of the spun yarn or drawn sheet. In FIG. 44, a syringe pump is adopted, in Example 53 a solvent bath is used, and in Example 54 steam condensation is used.

6. Storage of ultra-thin drawer nanofiber sheets The ultra-thin carbon nanotube sheet can optionally be pulled out and then applied to device construction without the need for storage. However, in some cases it is desirable to make rolls of such sheets and later apply these rolls to applications such as device construction.

The carbon nanotube (CNT) sheet is drawn from the forest, attached to a substrate film (eg, plastic, metal foil, porous paper, or Teflon® film), densified and wrapped around a mandrel. Illustrative examples of the potential of this process are given in Examples 23, 31, 32, and 45 for adhesive-free substrates, adhesive-coated substrates, and elastic substrates, and porous substrates, respectively. Such processes are schematically illustrated in FIGS. 53 and 54.

In Example 45, it is shown that carbon nanotubes are deposited on the required contour surface and densified on this surface so that the shape of the required contour surface can be retained within the shape of the sheet array of nanotubes. This mandrel can be the required contour mandrel. This application example includes a deposit of carbon nanotube sheets as a layer in a required contour composite (such as an aircraft panel), as a heating element for the required contour to prevent icing on an aircraft, or for energy storage and required contour. Allows supercapacitors of required contours to provide both structural components of car panels.

Element 5302 in Figure 53 is a nanotube forest prepared as described in Example 1. Element 5301 is a growth substrate, element 5303 is an nanotube sheet drawn from the forest, element 5304 is a substrate film, and element 5305 is an nanotube sheet attached to the substrate film. The attached nanotube sheet is densified using a liquid (element 5306), dried on a heater (element 5307) and then wound onto a mandrel. Here the rollers (2) are represented by white circles and the mandrel (3) are represented by filled circles. By repeating the process, the multi-walled nanotube sheet can be applied to the substrate film. A variant of that process is illustrated in Figure 54. Instead of liquid, liquid vapor (element 5406) is used to densify the collected sheet, and the densified sheet (element 5407) is wound onto the mandrel. The elements are the substrate for the nanotube forest (5401), the nanotube forest (5402), the CNT sheet (5403), the substrate film (5404), the CNT sheet attached to the substrate film (5405), and for the supply of steam. Heating system (5406), densified CNT sheet on substrate film (5407), mandrel for feeding substrate film (5408), roller for integrating nanotube sheet and substrate film (5409), and collecting mandrel (5410). ). Each roller in FIGS. 53 and 54 can optionally be replaced by a pair of rollers, one on each side of the laminated nanotube sheet and substrate film.

Importantly, the densified nanotube sheets manufactured by the equipment in Figures 53 and 54 are later rewound from the mandrel for yarn twist-based spinning to form self-supporting densified sheets. (See Example 37), or separation from the substrate film for mechanical transfer of selected portions of the nanotube sheet to other substrates (see Example 34). Similarly, the substrate may be an elastic film (or woven fabric) stretched prior to attachment of the nanotube sheet (see Example 32), or an adhesive coated substrate sheet (see Example 32). Stretching can be performed by controlling the relative rotation speed of the substrate feed and the winding mandrel of the substrate film / nanotube sheet and the rollers (or anti-rollers) between these mandrel.

Example 50 illustrates that the nanotube sheets are deposited on a substrate, densified by a liquid infiltration method, and then stripped from the substrate to give a self-supporting densified sheet arrangement. The importance of this illustration is that it allows the densified nanotube sheets to be stored on the mandrel and then removed from the sheet substrate (typically a plastic film carrier) for use. Is to become. A free-standing MWNT sheet (made in Example 21) in any of the three, five, or eight layers that remains in the drawer is placed on a substrate (eg, glass, plastic, or metal foil) to pour the liquid. It was densified using (using the method of Example 23). Plastic carrier substrates such as Mylar film were the most convenient. The desired width (or full width) of the densified sheet was easily stripped from the substrate using adhesive tape to initiate the process of removing the sheet. If the thickness of the densified sheet obtained by liquid infiltration of the sheet made in Example 21 is not greater than 30-50 nm thick (eg, as a result of using an advanced forest with sheet drawers), the carrier sheet. It is preferable to deposit more stacks than the one sheet above. This is because one 30-50 nm densified sheet is easily damaged during removal from the substrate.

According to Example 37, very thin densified carbon nanotube sheet deposits (less than 150 nm in thickness) can be rolled onto a mandrel for storage and possible shipping, and then separated for subsequent use. It is shown that it can be unfolded without or on a carrier sheet (as in the Mylar film in Example 50) without supporting the nanotube sheet.

7. Chemical and physical modifications before and after the production of threads, sheets and ribbons Various methods can be effectively adopted in the embodiment of the invention of modifying nanofibers either before or after drawing / plying or sheet drawing. Such modifications allow, for example, optimizing friction between fibers for twisting, creating covalent bonds between fibers for either yarn or ribbon, and electrical insulation of electrically conductive nanofiber yarns. The result is a variety of benefits (such as by the post-spinning chemical derivatization process over MWNT). Chemical derivatization, physical derivatization, surface coating, or dopant insertion can pull out and twist yarn before and after spinning, or before and after drawing and twisting, or to precursors in front of articles such as articles or woven fabrics. After making it, it can be executed at. Particularly preferred methods for modifying carbon nanotubes between nanotube forests are vapor phase reactions, plasma-induced reactions, or reactions and fluid extractions performed in the supercritical phase. This is because these methods generally preserve the nanotube alignment better inside the nanotube forest than the solution or melt phase method. More specifically, fluorination of carbon nanotubes with fluorine gas and plasma-induced surface derivatization are useful. The use of these processes for all types of yarns has not been previously recognized and they have not been applied to yarns, but provide useful reaction conditions and plasma-induced derivatives for the fluorination of carbon nanotubes. .. For example, European Journal Solid State Inorganic Chemistry 33,831 (1996) by T. Nakajima, S. Kasamatsu and Y. Matsuo; Chem. Phys. Lett. 296,188 (1988); and J. Phys. Chem, B103 4318 (1999) by ET Mickelson et al. ); And J.Phys.Chem.B105, by Q.Chen. Etc. 618 (2001). Other useful methods that can be used for the chemical derivatization of carbon nanotubes are Accounts of Chemical Research 35,1096-1104 (2002) by VNKhabasheshu et al.; Accounts of Chemical Research 35,1096-1104 (2002) by YPSun et al.; It is described in Accounts of Chemical Research 35, 1087-1095 (2002) by S. Niyogi et al. Many of these methods reduce the length of single-walled nanotubes, so there is an advantage in applying these methods to double-walled and multi-walled carbon nanotubes.

For example, the nanofibers in the nanofiber forest used for drawing and twisting nanofiber yarns are optionally coated with a hydrophobic material such as poly (tetrafluoroethylene). One such method of coating nanofibers is CF, which polymerizes poly (tetrafluoroethylene) on the surface of individual nanofibers.₂Hexafluoropropylene oxide is decomposed (hot filament CVD) on a heated filament at about 500 ° C to form radicals (see KKSLau et al., Nano Letters 3,1701 (2003)). The associated hot filament CVD can be used to provide coatings of other polymers such as organosilicon and fluorosilicone. The result of drawing and twisting these hydrophobic nanofibers from the nanofiber forest is a superhydrophobic nanofiber twisted yarn useful for water repellent fabrics and chemical protective clothing. Since the insulating poly (tetrafluoroethylene) coats the surface of the individual nanofibers (and thereby blocking electronic transfer between the fibers), such an electrically insulating coating is of its original electrical conductivity. Useful for producing less conductive twisted yarn from nanofibers.

Applying this and related coatings to already drawn and twisted fibers allows the nanofibers to retain their electrical conductivity. This is because the contact between the fibers takes place between drawing and twisting and the coating process can be performed without blocking these contacts. Selectively preferred, withdrawal and plying, because the application of tensile stress to the draw and plying yarn minimizes any reduction in the electrical conductivity of the yarn caused by the nanofibers coated with the insulating material. Used while coating the fiber with insulating material (including solid electrolyte). The advantage of coating the nanofibers in the yarn drawn and twisted with an electrical insulating material after such a drawing and twisting process is that the yarn has high electrical conductivity in the yarn direction and is insulating in the lateral direction. Is to become an insulating material coated wire.

Various useful methods for chemically and non-chemically functionalized nanofibers for various applications have been described in the literature and these methods are applicable to the nanofiber twisted yarns of the embodiments of the present invention ( See YL et al., J. Materials Chemistry 14,527-541 (2004)). The application of these and similar methods is performed on the preliminary major states of the spinning process, the major states of the spinning process, the spun yarn, the spun twisted yarn and the yarn assembly (as in textiles). ..

Insulation-coated such twisted yarns containing highly electrically conductive nanofibers such as carbon nanotubes are particularly versatile, eg, wire in electronic fabrics (clothing by providing the possibility of electrically heatable garments). Can be used for comfort control), and is useful in a wide range of applications such as insulated wires for transformers, magnets and solenoids.

Since the nanofiber yarns in the hands-on form of the invention can be knotted without loss of strength, the annotts, which are slip knots, can increase the yarn toughness measured on a weight basis. A slipknot is an unknot that pulls out the end.

Insertion of either individual slipknots or sequences of slipknots provides a selectively preferred method for increasing weight toughness to nanofiber yarns. Similarly, insertion of either individual slipknots or sequences of slipknots provides a selectively preferred method for altering the stress-strain curve of the nanofiber yarn in a useful way. When all of the slip knots in the nanofiber array are pulled out (which eliminates the contribution to mechanical energy and thread toughness), the stress-strain curve of the original star yarn approaches that of the annotted nanofiber yarn.

8. Composite formation using nanofiber threads, sheets and ribbons, and composite and non-composite applications Nanofiber yarns for nanotube spinning can be coated with a variety of inorganic and organic materials either before or after the twisting process. The purpose of this coating is to provide a friction aid to enhance the insertion of the twist, to give the twisted yarn a special function, or to combine these goals. In some cases, these nanofiber coatings can fill fractions of any size of yarn volume. However, if the filling rate is high, and if the material used for filling has mechanical properties that interfere with the twisting process, it is preferable to perform high filling after the initial twist insertion.

(a) Nanofiber yarn / electrolyte composite material Since stranded yarns are useful in electrochemical applications that utilize the extremely high surface area of nanotubes, a preferred embodiment of the invention provides a step in which the stranded yarns of the nanotubes are infiltrated with a solid or gel electrolyte. Examples of such applications are electromechanical artificial muscle threads, electrochromic threads, thread supercapacitors, and thread batteries. Solid-state electrolytes can also be used advantageously as such electrolytes enable thread-based electrochemical devices in the all-solid-state state.

Selectively more preferred organic-based solid-state electrolytes are polyacrylonitrile-based solid-polymer electrolytes (potassium, lithium, magnesium, or copper perchlorate, LiAsF.₆And LiN (CF)₃SO₂)₂) And ionic liquids in polymer matrices, which can provide a wide range of redox stability and a high cycle life of electrochemical processes. Selectively preferred gel or elastic solid electrolytes include polyethylene oxide copolymers containing lithium salts (due to redox stable windows, high electrical conductivity, and achievable elastic properties), and random copolymers of poly (epicrolhydrin). -co-ethylene oxide) based electrolyte, phosphate-containing nylon (such as nylon 6, 10, or nylon 6), and hydrated poly (vinyl alcohol) / H₃PO₄Can be mentioned. Another selectively preferred gel electrolyte is the lithium salt (LiClO).₄Etc.) and polyethylene oxide and polyacrylonitrile-based electrolytes with ethylene and propylene carbonate plasticizers. So-called "polymer in salt" elastomers (SS Zhang and CA Angell, J. Electrochem. Soc. 143, 4047 (1996)) are also selectively preferred for lithium ion based devices. They have very high lithium ion conductivity, elastic properties, and a wide redox stability window (Li).⁺This is because it provides 4.5-5.5V) for / Li.

Selectively preferred electrolytes for high temperature device applications include lithium ion conductive ceramics based ionic glass (superionic glass), ion exchange β-alumina (up to 1000 ° C), CaF.₂, La₂Mo₂O₅(Approximately 580 ° C or higher) and ZrO₂/ Y₂O₃(Up to 2000 ° C). Other selectively preferred solid-state inorganic electrolytes are Agl, AgBr, and Ag.₄Rbl₅Is. Some proton-conductive electrolytes that are useful in embodiments of the invention as solid-state electrolytes include, among other possibilities, Nafion, S-PEEK-1.6 (sulfonated polyetheretherketone), S-PBI ( Sulfated polybenzimidazole), and nylon, polyvinyl alcohol, polyacrylamide, and polybenzimidazole (such as poly [2,2'-(m-phenylene) -5,5'-benzimidazole]).

(b) Composites and additives to enhance electrical conductivity Additives that enhance the electrical conductivity of the nanofiber yarns of the embodiments of the invention are of particular importance. Preferred materials for increasing electrical conductivity include: (1) elemental metals and alloys, (2) electrically conductive organic polymers, and (3) conductive forms of carbon. These additives can be added to the nanofiber yarn for the synthesis or processing of these materials in a variety of known methods. For example (a) chemical reactions (eg, conductive polyaniline or polypyrrole, electrodeless plating of metals, thermal decomposition of polymers such as polyacrylonitrile to make carbon) (b) electrochemical methods for conductive threads ( For example, electrochemical polymerization of aniline or pyrrole to make conductive polymers and electroplating of metals, and (c) physical deposition methods (eg, metal deposition, soluble conductive polymers from solutions or precursors thereof). Methods such as body infiltration, infiltration of colloidal solutions of metals or conductive polymers, or melt infiltration of metals). Preferred conductive organic polymers for infiltration of nanofibers into twisted yarns include substituted and unsubstituted polyaniline, polypyrrole, polythiophene, polyphenylene, and polyarylene vinylene. Synthetic routes of conductive polymers suitable for preferred embodiments are well known and are described, for example, in the Hnadbook of Conducting Polymers, Second Edition, Eds. TASkotheim et al. (Marcel Dekkar, New York, 1998).

Diamond, diamond-like carbon and other sp³Hybrid carbon (sp²And sp-hybridized carbon can be mixed), carbon insulation forms are effectively adopted. Because they provide both the electrical insulation of the conductive nanofiber yarn and the substantial contribution of the mechanical properties of the yarn. The infiltration or coating of electrically conductive nanofiber yarns using these carbon insulating forms is a solid precursor that is selectively infiltrated, preferably by a CVD process or using thermal or thermal and pressure treatment. Depends on the state reaction. Typical methods that can be employed for the formation of such forms of carbon on or inside the yarn are (a) AERingwood, Australian Patent No. WO 8807409 (1988), (b) YSKo, et al., J. of Materials Research. 36, No.2,469-475 (2001) and (c) J.Qian et al., J.Mat.Sci.17,2153-2160 2002).

For carbon nanofibers, the deposition of palladium and palladium alloys (chemically or electrochemically, or by evaporation or sputtering) results in low resistance ohm connections between nanofibers and between nanofiber threads and other materials. Especially effective. The use of this metal for enhancing electrical connectivity in nanosized electronic devices is described by A. Javey, J. Guo, Q. Wang, M. Lunstrom and HJ Dai in Nature 424,654-657 (2003). The formation of palladium hydride by hydrogen absorption can be employed to regulate the work function to minimize contact resistance between carbon nanotubes and between them.

(c) Structural composite material Polymer additives for twisted and false twisted yarns that are particularly preferred for the production of yarn composites include polyvinyl alcohol; poly (phenylene terephthalamide) resins (eg, Kevlar® and Twaron®); poly (registered trademarks). Para-phenylene benzobisogizazole (PBO); Nylon; Poly (ethylene terephthalate); Poly (para-phenylene benzobisthiosol); Polyacrylonitrile; Poly (styrene); Poly (etheretherketone); and Poly (vinylpyrrolidone) ). A type of epoxy such as that used to form a graphite-epoxy composite is also preferred in embodiments of the invention.

Pyrolytic polymers can optionally be pyrolyzed in twisted yarns, false twisted yarns, or nanofiber yarns densified in the liquid state to produce durable, highly conductive components. Heat treatment and pyrolysis (eg, heat setting in an oxidizing atmosphere and further pyrolysis of polyacrylonitrile in an inert atmosphere) are preferably performed while the nanofiber strands are under tension. This tension state is preferable, which results in fiber extraction during at least part of the pyrolysis process. Pitch is also a particularly preferred yarn additive for stretch-accelerated pyrolysis resulting in carbon matrix / nanotube yarns. Nanofiber yarns containing materials that can be pyrolyzed to produce carbon (such as pitch or polyacrylonitrile) are preferably either false twisted or densified in the liquid state. This is because high twisting limits the ability to obtain fiber draws during pyrolysis and is not desirable.

Due to the importance of drawing out to reinforce the matrix polymer and improve the properties of the material to be pyrolyzed, and the observation that twisting reduces the drawing out of nanofiber yarns, false twisted yarns are especially of yarn composites. It is useful for optimizing the properties that can be achieved.

Structural materials used to generate friction, especially friction materials used for brakes on land vehicles and aircraft, benefit from the adoption of carbon nanotube threads and seats of the embodiments of the invention. Selectively preferred, these structural composites are carbon-carbon composites. These carbon-carbon composites include either a nanofiber sheet, a pyrolysis of organic material infiltrated into an array containing nanofiber threads, or an array containing both nanofiber sheets and nanofiber threads. It is preferably produced during the process.

When used in brakes, the nanofiber sheets are preferably oriented substantially parallel to a friction surface, such as the disc surface of a brake on a land vehicle or aircraft. Optionally, these nanotube sheets are at least in substantially orthogonal directions, with reinforcing threads or fibers, optionally including either graphite fibers or threads, or the nanotube threads of embodiments of the invention. Crossed. This stitching process can be performed using methods well known in the art.

The formation of carbon-carbon composites using the sheets and threads of the nanotubes of the present invention can proceed in a manner similar to the conventional techniques for carbon-carbon brake materials, similar to those employed for oxidative protection. Additives are available. Selectively preferred materials for pyrolysis for forming the matrix components of carbon-carbon brake materials are phenolic resins, polyacrylonitrile, and similar materials known in the art.

The vapor phase pyrolysis step can optionally be performed, for example by using natural gas as a component of the gas. Numerous resin and gas infiltration steps are effectively employed to reduce void space and optimize performance.

(d) Uses of composite and non-composite materials Various applications made possible by the high strength of the sheet and ribbon are described in Examples 6 and 27. The inventors here have already used Mylar® and Kapton® films here for ultra-lightweight aircraft and have been proposed for solar sailing vessels for space applications. Strength ~ 160MPa / (g / cm)³) (DE Edwards et al., High Performance polymers 16,277 (2004)) and ultra-high strength steel sheet (~ 125MPa / (g / cm)³)) And aluminum alloy (~ 250MPa / (g / cm)³) Provides comparable or higher density normalization strength.

Due to the inventor's high strength against nanofiber sheets, ribbons, and threads, preferred applications include membranes, diaphragms, solar parachutes, tents and other living room structures, ultra-lightweight aircraft, micro and macro aircraft, pneumatic support. cloth (e.g., dome, balloons, and other inflatable structure), parachutes, and ropes (e.g., perforated on the connecting object in anchoring and space marine vehicle (tether) for ones) that can be mentioned is shown .. As an alternative or complement to the use of air supports, nanotube-based sheets and ribbons and nanotube-based fabrics are mechanically tensioned, for example using metal tensioning elements.

The threads and sheets used can optionally be overlaid. For example, the oriented nanofiber sheets of the embodiments of the invention (see Examples 28 and 27) are optionally laminated together to produce a laminated sheet structure in which not all sheets have the same nanofiber orientation direction. it can. In fact, the nanofiber sheets in the lap sheet structure can be lapped to produce a lap sheet that is anisotropic with respect to in-plane (ie, in-sheet orientation).

The nanofiber thread or sheet may optionally contain another functional material support. For example, infiltrated or overcoated materials are beneficial for reducing or eliminating gas permeability due to membranes, diaphragms, expansion structures, and pneumatically supported structures. These coated or infiltrated nanofiber-based structures include sheets of nanotubes, ribbons, and fabrics incorporating nanofiber threads, as well as potentially others. Threads, ribbons, and sheets and matrix materials infiltrated with polymers, metals, and other binders are particularly beneficial to provide strength enhancement as well.

These carbon nanotube sheets are particularly promising for use as solar sailing vessels, as the mechanical weight strength of carbon nanotubes surpasses that of Mylar developed for solar sailing vessels. While it is difficult to make ordinary polymer films thin enough, we have created very thin (50 nm thick) nanofiber sheets in which a 4 ounce sheet can cover 1 acre.

Such or thicker sheets of embodiments of the invention can optionally be stacked for the purpose of making a durable solar sailing vessel in all directions in the plane. The stability of the nanotubes to extreme radiation and heat, as well as the exceptionally high thermal diffusivity of these sheets (which promotes temperature equilibrium when the sheet area and sheet sides are exposed to different thermal conditions). Would be particularly useful for solar sailing applications.

Due to its favorable deployment performance, a solar sailing vessel with a petal configuration containing nanofiber sheets, nanofiber yarns, or a combination thereof is selectively preferred. A solar sailing vessel with such a petal configuration is named after a configuration similar to the open petal arrangement of the solar sailing vessel's wing plate arrangement. Teaching the geometry of such solar sailing vessels is in the literature. Recently, a type (consisting of a metal-coated Myra) was launched into space on a missile, but the launch into space was unsuccessful.

A selectively preferred configuration for a solar sailing vessel with a petal configuration is one that includes at least a plurality of substantially triangular petals spliced at the vertices of a triangle. The angle of the triangle at the apex where the triangles are joined is preferably greater than 15 ° and less than 120 °. The number of rectangular petals on a solar sailing vessel is also preferably at least three.

Nanotube sheets can be used for solar sailing applications without coating or lamination, while nanofiber sheets are selectively preferred to be highly reflective, which is a thin metal overcoat deposit or high reflectivity of nanofiber sheets. It can be achieved by laminating with the materials of. Overcoating of such highly reflective materials can optionally be performed as an infiltrated nanotube sheet, such as a polymer infiltrated sheet.

The high strength of carbon nanotube sheets and carbon nanotube-based fabrics, as well as the achievable toughness, means they can be incorporated into tires as tire cord fabrics and optionally indicate tire pressure and operating conditions under conditions of use. It can be used to give the response of the sensor. The method of incorporating nanofiber sheets, nanofiber fabrics, and nanofiber yarns into a tire, such as a rubber tire, can be like the method used to incorporate ordinary tire cords.

These mechanical properties allow them to be used in bulletproof composites (including bulletproof fabrics), cutting-resistant gloves and other clothing, spacesuits, and other applications such as those incorporated into protective clothing for moon or planetary flight. It will be possible. The high thermal conductivity and thermal diffusivity of nanotube threads, sheets or fabrics make it a variety of garments, such as for temperature controlled garments (such as spacesuits and protective clothing for exploration of the moon, planets, and other objects in outer space). Useful for applications.

9. Assembly of twisted nanofiber threads, sheets, and ribbons with other fibers The twisted yarns, false twisted yarns, and solution densified nanotube yarns of the embodiments of the invention are optionally combined with a non-woven fabric to combine the cost advantages of the non-woven fabric with the mechanical and electrical properties that can be achieved over the nanofiber twisted yarn. Structures can be manufactured. Various combinations are beneficially adopted. For example, stranded nanotubes are embedded within the non-woven fabric to improve the mechanical properties of the assembly (such as non-woven fabrics manufactured by electrostatic spinning), or nanofiber stranded yarns are used to stitch the non-woven fabrics. The advantage of incorporating electrically conductive nanofiber twisted yarns inside an electrically insulating non-woven fabric is that these non-woven fabrics can insulate the electrically conductive elements in the twisted nanofiber-based electronic circuit. Optionally, the non-woven fabric can be entangled using means such as lateral penetration with a water jet or needle bed.

The electrically conductive nanofiber sheet of the embodiment of the invention can optionally be used as either a receiving electrode for electrostatic spinning or a coating material for this electrode. In both cases, the beneficial result is the product, which is a laminate of electrostatically spun yarn and the nanofiber sheets of the embodiments of the invention.

Electrically insulating fibers and threads can be spirally twisted around electrically conductive nanofiber twisted threads, optionally to provide electrical insulation and other desired properties. Similarly, nanofiber twisted yarns can be twisted around conventional yarns and yarns using equipment commonly used to produce morphologically similar structures from conventional yarns and fiber structures. .. Such methods include adaptations of core and lap spinning to conventional ring spinning frames.

In Example 53, a twist-based method for producing fiber composites of two different fibrous materials, one containing electrically conductive carbon nanotubes and the other containing electrically insulating cellulose microfibers. Is illustrated. Similarly, this example illustrates a method of providing either insulating microfibers or conductive carbon nanotubes to the outer surface of the twisted yarn. In addition, this illustration shows how the carbon nanotube yarn is coated with an insulating layer. Similarly, by replacing the cellulose sheet with a similar sheet containing meltable polymer microfibers (such as polypropylene or polyethylene-based non-woven paper), the method of Example 53 is by heating with heat or microwave. It can be used in the production of polymer / nanotube composite yarns in which either twisting or false twisting is applied prior to melting the polymer on the surface of the nanofibers in the yarn. This illustration uses a tissue paper / nanotube deposition composite contoured using the method of Example 45. A 3 mm wide ribbon is cut from the composite deposit parallel to the nanotube orientation direction and twisted to give a medium strength yarn. Insulating cellulose microfibers or electrically conductive carbon nanofibers (depending on the direction of twist) on the surface of the twisted yarn for delineation (with nanotube fiber orientation in the circumferential direction) on an apparently elliptical mandrel. We have found that it appears in.

Woven structures used in a wide range of applications include nanofiber twisted yarns used for either full or partial warp or full or partial weft. Insulating yarns or fibers can separate electrically conductive nanofiber twisted yarns in warp yarns, weft yarns, or both, just as they electrically separate conductive nanofiber twisted yarns. These conductive yarns may optionally (to avoid unwanted electrical contact due to bending of the fabric) laminate or insulate an insulating fabric on the fabric side where the conductive nanofiber twisted yarn is exposed. It can be separated by giving a coating. Instead, conductive nanofiber twisted yarns compared to insulating yarns or fibers that separate these conductive yarns so that insulation is provided by embedding the conductive nanofiber yarns in the fabric volume. Can have a small diameter. For this purpose of preventing short circuits of uninsulated conductive nanofiber yarn wires, electrically conductive nanofiber yarn wires are selectively preferably at least 5 times the diameter of the electrically conductive nanofiber yarn wires. It is incorporated into a woven fabric woven with insulating threads having.

Figure 40 shows a laboratory-made yarn that combines wool fibers and nanotube components in a twist-based process. The advantage of such an assembly is that it combines the attractive properties of wool with that of carbon nanotubes. For example, carbon nanofiber components can provide the electrical conductivity required for yarn applications for electrical heating, and wool components can provide advantageous properties of wool, such as the ability to absorb sweat. ..

After the initial nanofiber yarns, sheets, or ribbons are made by the solid state method, additional to the nanofiber threads, ribbons, and sheets spun in the solid state by various beneficial methods. Carbon nanotubes or other nanofibers (referred to as secondary nanofibers) are incorporated. One method is to allow CVD-based growth on top of this catalyst by adding a catalyst to these prefabricated materials. Another method is to add a catalyst by thermal decomposition of the metal-organic compound during the CVD growth of the secondary nanofibers. These methods are particularly useful for sheets, ribbons, and yarns of carbon nanotubes spun in the solid state, and especially for the CVD growth of secondary nanofibers that become carbon nanotubes.

Such additional addition of CVD-grown nanotubes to preformed nanotube sheets, ribbons, and threads results in the formation of useful hierarchical structures, which include nanofibers, bundles of nanofibers, and more. Nanofibers grown from catalysts on large nanofiber assemblies are cited as useful. Benefits are gained from such secondary nanofibers over preformed threads, ribbons, and sheets, including enhanced thermal and electrical conductivity.

Alternatively, a secondary nanofiber can be added to the preformed nanofiber sheet of the embodiment of the invention by a filtration process of the type typically used for forming nanotube sheets on a filtration membrane. Other conventional filtration membranes can also be employed to support preformed nanofiber sheets during the filtration process, although such support is particularly beneficial if the preformed nanotube sheets are very thin at 30 nm. In fact, the nanofiber sheet is the filtration membrane.

10. Application of nanofiber threads, ribbons, and sheets (a) Application to textiles The amazing properties of nanotube yarns obtained from the implementation results of embodiments of the invention are particularly useful as applications of nanotube yarns to either a small number or the majority of components in two-dimensional or three-dimensional fabrics, including electronic fabrics. Is. Surprisingly, we have found that the use of the processes of the present invention can result in high thermal or high electrical conductivity in combination with high strength and high toughness. The small diameter yarns achieved (1 micron) are more than 10 times lower than previously reported continuous fibers or yarns containing only regular woven yarns and nanotubes.

The highly conductive nanofiber strands can be woven into the fabrics used in the garment and are collected, for example, by health information, wearer position and body movements, and sensor devices in the wearer or garment. It is useful as an antenna used to carry voice communications and other data, such as information to be used. The configuration adopted by such an antenna is basically the same as that of a conventional antenna, except that the antenna of nanofiber yarn can be woven or sewn into a garment fabric.

In addition, electrically conductive nanofiber stranded yarns can be beneficially employed to turn garment fabrics (and fabrics used in applications such as tents) into large area acoustic arrays for noise detection and positioning. The nanofiber yarn can be connected to a microphone in the fabric and may be as simple as a polled ferroelectric polymer located at the intersection between the nanofiber yarns in the fabric. These intersections do not necessarily have to be nanofiber yarns, but are selectively preferably between nanofiber yarns that are at least substantially orthogonal, such as the warp and weft yarns of a woven fabric. Polling of the ferroelectric coating on the nanofiber yarn can be done either before or after weaving the nanofiber yarn assembly. However, the polling direction of the ferroelectric material is preferably orthogonal to the length direction of the yarn, and the polling step is selectively performed after the woven fabric is manufactured. The polling processing direction may be either in the plane of the nanofiber yarn or orthogonal to the plane, depending on the case. However, it is selectively preferred to be orthogonal to the plane of the fabric, or to the local plane of the fabric if the fabric is not.

Replacing metal wires in electronic fabrics with nanotube threads provides important new functionality, such as the ability to act as artificial muscle and store energy as fibrous supercapacitors or batteries. The polymer-free MWNT yarns of the present invention provide twice the strength of nanotube fibers used in artificial muscles (RHBaughman, AAZakhidov, and WAde Heer, Science 297,787-792 (2002)), and the polymers are intercalated. MWNT yarns provide 100 times higher electrical conductivity than that of cohesive-spun SWNT / PVA fibers used to make fiber-state supercondensers (AB Dalton et al., Nature 423,703 (2003)).

Micron or thinner threads or thinner sheet thicknesses exemplified in embodiments of the invention and the low visibility found in these thinnesses, as well as the high electrical conductivity illustrated in certain constructs (such as carbon nanotubes). Reflecting this, the threads and sheets of the embodiments of the present invention are beneficially employed, for example, as transparent and poorly visible substrate materials for making electrical connections and interconnects. The resulting transparent conductive electrodes include liquid crystal displays, light emitting displays (both organic and inorganic), solar batteries, switchable transparent windows, microlasers, light modulators, field emission devices, electronic switches, and optical polarizers. It is important for applications such as. Inorganic electrodes such as ITO (indium tin oxide) deteriorate in quality due to bending and are expensive to apply or repair. An embodiment of the present invention solves these problems.

The stranded yarn of the embodiments of the invention is suitable for fabric-like keyboard switches for electronic fabrics due to the extraordinary mechanical strength, abrasion resistance, and durability against deterioration of all these properties to bear against knotting. .. The pressure switch of the embodiment of the invention is (a) a woven fabric containing electrically conductive nanofiber stranded yarn (such as carbon nanotube stranded yarn) that supplies the first switch contact, and (b) the first to the first switch contact. Electrical connection of (c) second electrical connection made to the material which is the second switch contact, (d) of the first and second switch contacts when proper pressure is not applied to the switch. Insulating material that blocks direct or indirect electrical conduction between (and thereby between the first and second electrical connections), (e) first and second when appropriate pressure is applied. Includes means for forming electrical conduction between the two switch contacts.

In one embodiment of the invention for such a keyboard switch, electrically conductive nanofiber strands are woven into a first woven fabric, resulting in an electrically conductive surface region of the woven fabric. This fabric, which has a conductive surface area that acts as a first switch contact, is provided with a second electrically conductive surface by means of an insulating spacer sheet (such as an insulating fabric, or an insulating fabric fiber or thread of suitable composition). Is separated from. This insulating material is spread only over the contactable area between the first switch contact and the second electrically conductive surface, resulting in the first switch contact due to the pressure applied at approximately right angles to the switch surface. An electrical contact is provided between the and the second electrically conductive surface. This second electrically conductive surface can be a second switch contact. Instead, this second electrically conductive surface is electrically joined between the first and second switch contacts to provide an electrical path between these switch contacts due to pressure-induced bending of the sheet or fabric. Can be contacted. In the latter case, the second switch contact may be in the electrically conductive region of the same fabric where the first switch contact is located.

In the above switch, one or both of the electrically conductive fabrics can be replaced with an electrically conductive nanofiber sheet or sheet portion made by a solid drawing process. The nanofibers in the nanofiber sheet or sheet portion are selectively preferably carbon nanotubes, and these carbon nanotube sheets or sheet portions are selectively preferably derived from the carbon nanotube forest. The electrically conductive nanofiber sheet or sheet portion can optionally be attached to another electrically insulating woven surface. The advantage of such an attachment is that it provides mechanical support for the electrically conductive nanofiber sheet, especially if the electrically conductive nanofiber sheet is very thin and results in optical transparency. .. Such optical transparency is especially important to give maximum freedom in devising the appearance of the fabric.

The combination of incredible mechanical and electrical properties, especially useful in electronic fabric applications, allows the usual wires of these fabrics to be replaced by nanofiber twisted yarns. For example, the conductive nanofiber twisted yarn of the present invention can be used as a sensor and clothing wire that includes a liquid crystal display or a light emitting element (such as a light emitting diode). These nanofiber stranded yarns and especially carbon nanotube stranded yarns can replace the usual wires used in electronic textile applications described in IBM Systems Journal 39,840-860 (2000), such as ERPost, and similar methods. Can be employed to create device structures from ordinary wires and from these nanofiber stranded yarns.

The twisted yarn of the embodiments of the invention is a microdenier version of Velcro® that provides a permanent or easily removable interconnect by applying pressure between the opposing surfaces to create tight contact on these surfaces. Can be adopted to manufacture. In certain embodiments of the invention, the nanofiber stranded yarn provides a closed loop in the fabric base that interconnects with hooks on the mating surfaces. These hooks on the mating surfaces can be hooks, such as arrows, and when a fabric containing nanofiber threads is pressed onto an adjacent surface, the nanofiber threads loop around it. Made. Alternatively, the hook may be a cut loop of nanofiber yarn infiltrated with a rigid polymer, for example by infiltration of the polymer from a polymer solution or by a photopolymerization reaction of the infiltrated polymer. There are many advantages to using nanofiber stranded yarn as such for this application. By using tough, tough carbon nanofiber threads that engage strong hooks (such as diamond hooks manufactured by lithography), extremely tough interconnects are made between the mating surfaces, thereby with the mating surfaces. Very high thermal conductivity is given between (as a result of the high thermal conductivity of both carbon nanotubes and materials such as diamond). When the mating surfaces on both sides are electrical conductors, the mechanical connection between the two mating surfaces provides an electrical connection, which can be used, for example, to make an electrical connection of the electronic fabric. Furthermore, a closed loop and hook pattern (or mechanical equivalent) can be provided to assist the engaging process laterally aligning the two surfaces on both mating surfaces. Furthermore, the extremely small nanofiber yarn diameters described herein imply that this means of connecting surfaces (woven or solid) is applicable to the 100 micron scale for microcircuits. For example, in such applications, the thread loops are fixed in a solid polymer or metal and the opposing hooks are silicon, diamond, diamond-like carbon, plus.

(b) Knot-based electronics and other methods of manufacturing electronic devices from twisted or untwisted nanofiber yarns. The uses of the nanofiber twisted yarns of the present invention as electronic devices (particularly those found in electronic fabrics) are (1) demonstrated mechanical robustness and electrical conductivity and retention of these conductivity when the yarn is infiltrated, (2) Ability to change the electrical properties of yarn compartments by chemical modification or doping, (3) No deterioration of mechanical properties when nanofiber twisted yarns are knotted, (4) Inventions It is made possible by the various metallic, semiconducting, and metallic nanofibers available for carrying out the embodiments.

Approximate composition MoS_9-XI_XNanofiber stranded yarn made of superconductors such as nanofibers with (where X is between 4.5 and 6) can be used as superconducting wires for superconducting cables and magnets. Nb₃Nanofiber as Sn superconductor, MgB₂Superconductor (with superconducting transition temperature of about 39K), and carbon-doped MgB₂Superconductors are particularly preferred as nanofiber components for nanofiber stranded yarns of the embodiments of the invention which are superconducting (see Y.Wu et al., Advanced Materials 13,1487 (2001). Superconducting MgB by reaction with steam₂Nanowire growth is described). The advantages of using the methods of the embodiments of the invention are the high strength, high toughness of the stranded nanofiber yarns and the tight electrical interconnection between the nanofibers in these yarns.

The novel method of the embodiment of the invention described above provides a controllable pattern change in electrical properties along the length direction of the yarn, which is beneficial for the fabrication of electronic devices based on nanofiber yarn. Can be adopted. The present inventors describe here other novel methods that can be adopted for device fabrication using nanofiber yarns.

We refer to the first category of embodiments of the invention as knot-based electronic technology. This is because the knot structure is used in the manufacture of electronic devices. One strategy is knot-based lithography, which offers the potential for patterned deposition, reaction, or removal required to make electrical, fluid, thermal, or mechanical circuits or circuit elements. Thread densification at the knots (and, in some cases, differences in densification at different locations within the knots) is utilized to provide. These patterned deposition, reaction, or removal methods apply to single yarns, twisted yarns and yarns woven or otherwise assembled into the structure. Similarly, these methods for obtaining region-selective material deposition, reaction, or removal include gas; steam; plasma; liquid; knotted threads or thread assemblies, among other useful choices. Solution; fluid dispersion; supercritical fluid; melt; or exposure to conditions resulting in electrochemical deposition, electrochemical material removal, or electrochemical polymerization can be mentioned.

The simplest embodiment of these concepts is that for the twin yarn of FIG. 6 and the single yarn of FIG. 12, the tightly knotted yarn region has a higher density than the fiber unknot region. It can be understood by paying attention. This density difference makes the fiber knot region much more difficult to infiltrate with liquid, vapor or plasma than the yarn unknot region. For example, the selectively infiltrated agent may be a chemical used to transform the electrical properties of the infiltrated thread region, or for the uninfiltrated thread region, eg, chemistry. It may be a resist material that acts to protect the infiltrated area when the conversion of electrical properties is performed by physical or electrochemical doping or liquid, gas, or plasma-induced chemical conversion. After this process, the resist material is optionally removed.

At the knot inlet (1203), knot outlet (1204), and knot body (1201), due to the relative thread dimensions at the thread location (1202) removed from the inserted single knot by scrutiny in FIG. It is shown that a regional density difference that can be used for selective regional infiltration and reaction is given. The stray nanotubes seen in the photograph, migrating from the knot or other region of the knot, can optionally be removed chemically (eg, by passing the thread through an open flame). If applications such as field emission are desired, these stray nanotubes are selectively treated in different regions of the yarn by mechanical treatment or chemical treatment, including chemical treatment resulting in breakage of the nanofibers. Can be increased. Examples of such mechanical treatment are, for example, friction between the nanofiber stranded yarn and the rough surface or orifice, and sonication of the nanofiber stranded yarn (selectively preferably with tension applied to the yarn). Examples of chemical processes include oxidation in air during oxidizing acids, plasma oxidation, and thermal annealing, and surface fluorination, which is later reversed by thermal annealing.

Knots can be formed by any of the methods currently used in the textile industry. The type of knot formed depends on the size and nature of the particular structure required. One knot has a small knot length and can be used for compact applications when the yarn package is relatively small. For high volume applications where a wider range of knotting is required, loops can be formed using any of the currently established techniques such as braiding, blazing, embroidery, and then Tighten to the extent required for the application.

Differences in electrical conductivity for knot or unknot regions of electrically conductive threads (such as carbon nanotubes) are also used in lithography. One approach is to apply voltage pulses, or continuous, well-separated voltage pulses, to cause preferential thermal conversion or evaporation of electronic chemicals into the more resistant fiber regions. is there. Since the knot region generally has higher electrical conductivity than the unknot region, when a voltage pulse is applied, the temperature of the unnot region of the yarn selectively increases relative to the knot region of the yarn. On the other hand, the higher porosity of the unnotted region of the fiber is used to reverse this effect. The higher porosity of the yarn unknot region means that the temperature increase during continuous electrical heating is less than that of the yarn knot region.

Knotted nanotube twisted yarns are preferred for selective use of these yarns, some of which have been described above. For example, special types of knotted nanofiber strands, such as independently tied knots (called knot factors) that are assembled to partially or completely overlap the nanofiber strands, are also a selective application. Is preferable.

The nanofiber yarns of the embodiments of the invention can be patterned to selectively provide semiconducting, metallic or superconducting regions either before or after incorporating these yarns into the fabric. This patterning can be done by a variety of methods, for example, either (a) the application of well-known lithography or soft lithography, (b) inkjet printing, or (c) laser printing. These methods are selectively preferably multi-step, and various well-known patterning methods such as photopolymerization or electron beam-induced reactions of polymers; pressure-induced mass transfer; and deposition, removal, or conversion of materials. A combination of liquid, gas phase or plasma treatments is possible.

A method is adopted in which conductive threads are used as interconnects for self-organizing functional devices such as electronic chips. Such methods differ with respect to each other in the fabrics, the ability to create very small diameter electrically conductive threads, the ability to create woven structures containing precisely shaped push-down patterns, which can be produced by the methods of the embodiments of the present invention. The ability to insulate length is available. Functional devices (such as transistor chips) contain chips, using shape effects, changes in patterned surface tension, or (most preferably) a combination of these effects, and possible other self-organizing effects. It can be self-assembled on the woven fabric by depositing the fluid on the woven fabric. FIG. 16 provides a schematic representation of the woven structure that provides binding sites for functional devices (eg, substrate dissociative electronic chips), where the functional devices are docked with these docking sites from a liquid-based dispersion of particulate devices. Can be self-organized on top of the fabric. Element 1601 is an electrically conductive nanofiber stranded yarn that is insulated from all of what is depicted in the element. Element 1602 and all of similar shaped holes can be binding sites for functional devices.

Related methods have been adopted to self-assemble electronic chips on a flat or curved substrate in the form of a plastic sheet containing metal wires for interconnection (KDSchatz, U.S. Pat. No. 6,780,696; TDCredelle, et al. 6,731,353; JSSmith et al., 6,623,579; and 6,527,964; MA Hadley et al., 6,590,346; see GW Gengel, 6,417,025). The teaching of this prior art is to provide useful modifications to the embodiments of the present invention in which the nanofiber strands in the fabric are used in the electronic fabric together with other fabric components for fluid-based electronic chip self-assembly. Can be used. The various methods described in this prior art demonstrate means for connecting metal wires to self-assembling electronic chips and how these and related methods function to self-assemble on nanofiber yarns and fabrics. It will be apparent to those skilled in the art as to whether it is applied to provide interconnects with sex devices (such as electronic chips and microfluidic circuit elements).

(c) Wire applications Nanofiber yarn can be used as wires and wire cables that carry high currents. Carbon nanotube twisted yarns, and in particular such yarns containing conductivity-enhancing aids, are particularly useful for carrying current. The advantages obtained with these carbon nanotube stranded yarns are high current transport capacity, high temperature stability, and the absence of electromigration effects that cause breakage of small diameter copper wires. The low weight and high mechanical strength of these nanofiber strands makes them particularly useful for aerospace and outer space applications where weight is of particular importance, and it is useful to employ wiring to provide mechanical reinforcement. Useful for applications. Other possible applications are, for example, as power cables and as windings for magnets, transformers, solenoids and motors, and for these devices incorporated into fabrics.

Electrically conductive bonding between threads or between threads and other materials can be performed using conductive gels (eg, silver paint, etc.), knotting, or mounting.

(d) Electrical device applications-supercapacitors, batteries, fuel cells, artificial muscles, and electrochromic articles Due to the highly achievable porosity of the twisted nanofibers and the high electrical conductivity illustrated here for specific twisted yarns, such as both before and after infiltration with the electrolyte of carbon nanotube twisted yarns, these Twisted yarns are useful as electrodes for yarn-based electrochemical devices that use either electrochemical double-layer charge injection, Faraday charge injection, or a combination thereof. These devices can utilize either the electrolyte in the liquid state, the electrolyte in the solid state, or a combination thereof (see the discussion of electrolytes above).

Examples of the twisted electrochemical device of the present invention include a supercapacitor that has a large capacitance compared to the capacitance of a normal dielectric-based capacitor, and an electrochemical that can be used as an artificial muscle of a robot. Actuators can be mentioned. Similar to ordinary capacitors, carbon nanotube supercapacitors (AB Dalton et al., Nature 423,703, (2003)) and electrochemical actuators (RHBaughman et al., Science 284,1340, (1999)) were separated by an electrically insulating material. It contains at least two electrodes that are ionically conductive in an electrochemical device. The capacitance of a normal flat sheet to a capacitor depends in inverse proportion to the isolation distance between the electrodes. In contrast, electrochemical. The capacitance to the device depends on the isolation distance between the charge on the electrode and the pair of charges in the electrolyte. Compared to the micrometer or higher isolation distance of a typical dielectric capacitor, this isolation distance is Due to the approximately 1 nanometer relative to the nanotubes in the electrode, the high surface area of the nanotubes with access to the electrolyte provides a very large capacitance.

These capacitances (typically between 15 and 200 F / g, depending on the surface area of the nanotube array) result in a large charge injection when only a few volts are applied. This charge injection is used for energy storage in nanotube supercapacitors and also results in expansion and contraction of electrodes capable of performing mechanical work in electromechanical actuators. Ultracapacitors with carbon nanotubes are used in applications that require higher power performance than batteries and higher storage performance than regular capacitors, such as hybrid electric vehicles that can provide rapid acceleration and electrically store braking energy. It can be used for various purposes.

The configuration of the strands for an electrochemical device that can be used as a supercapacitor, artificial muscle, or battery is shown in Example 18. These twisted yarns can be incorporated into the woven fabric as processed yarns. Incorporation of cohesive spun nanofibers as supercapacitors in textiles has been previously shown (see AB Dalton et al., Nature 423,703 (2003)), but these processed yarns are required to enhance mechanical properties by inserting twists. It had neither the degree of twist nor the high ratio of nanofiber length to fiber circumference. Similarly, these prior art fibers had about an order of magnitude lower electrical conductivity than the highly twisted carbon nanotubes of the embodiments of the invention.

Various methods can be employed to effectively employ the nanofiber yarns of the embodiments of the invention in thermochromic devices, including those woven into electronic fabrics or otherwise arranged. One method is to use nanofiber stranded yarn as a heating element to cause color change in thermochromic materials such as liquid crystals that have been overcoated or otherwise incorporated into nanofiber yarn.

Another method is to utilize the electrochemically induced color change of the electroconducting nanofiber yarn electrodes infiltrated or coated with electrolyte. For this method, the counter electrode may be another twisted nanofiber that contacts the same electrolyte as the working electrode. But there are other useful possibilities. For example, counter electrodes are electrically conductive coatings on fabrics that are separated from nanofiber electrodes twisted by an ionic conductive electrolyte that is required to both avoid short circuits between the electrodes and provide an ionic path. It may be. Electrochemically induced color changes in nanofiber yarns in either the infrared, visible or ultraviolet regions involve either Faraday processes, non-Faraday charge injections, or a combination thereof. In some cases, electrically conductive nanofiber strands (or nanofiber strands containing conductive polymer nanofibers) overcoated with a conductively induced polymer provide color change for color change applications, and especially in electronic fabrics. Preferable as a thread electrode. Twisted yarns of carbon nanofibers are particularly preferred as electrodes that change color in the case of either Faraday-like or non-Faraday-like electrochemical charges, as the case may be. These color changes occur for carbon nanotube fibers in the useful region of infrared light, which is not absorbed by the atmosphere.

When these chromic materials are used, it is possible to obtain an electronic woven fabric that gives a pixelated color change. A method of electrically addressing individual pixels, which is widely used in liquid crystal displays, is well known and the same method can be used herein. For example, by applying an appropriate voltage between the ends of orthogonal yarns in a woven fabric, the thermochromic material that separates these yarns is selectively heated and has much lower electrical conductivity than that yarn. Given.

The conductive nanofiber twisted yarn is particularly useful as a fuel cell electrode filled with an electrolyte and containing a catalyst. Due to its strength, toughness, thermal conductivity, and porosity, carbon nanotube twisted yarns are preferred constructs for fuel cell applications. Fuel cell electrodes may include single or synthetic yarns (along with permeable electrolytes and catalysts such as Pt), or may include an array of twisted yarns, especially those woven (or constructed) into the fabric.

FIG. 104 schematically illustrates a fuel cell of an embodiment of the invention configured in the form of a thread-sized and thread-shaped device woven into a fabric, or as a device of larger diameter. The hydrogen electrode (10402) of the carbon nanotube thread may be an assembly of the nanotube thread, coated with a solid electrolyte (10403), in close contact with this electrolyte, and the electrolyte is of the surrounding braided nanotube thread. It also comes into close contact with the oxygen electrode (10401). Both 10401 and 10402 contain sufficient nanoporous void space, where air (or oxygen) contacts 10401 and hydrogen is transported through 10402. Typically, it is preferred that the Pt or Pt alloy catalyst be in the contact area between these gases and their respective electrodes. Hydrogen fuel is transported through the porous region of the nanotube thread electrode 10402 and oxygen (or air) is delivered to the oxygen electrode 10401. Hydrogen fuel can optionally replace alternative fuels such as hydrazine or methanol.

It is important to provide reliable fuel access to electrode 10402. Several methods can be used: internal fuel storage, external fuel storage, and intermittent internal and external fuel storage. The method of external storage is to have a fuel source (such as hydrogen) separated from the thread fuel cell. The method of achieving internal storage is to store the hydrogen producing fuel in the hydrogen electrode of the thread of the fuel cell. In both cases, fuel storage and fuel access to the electrodes are inside and through the hollow region of the yarn electrode 10402 (such as the hollow central region of the braided yarn), or the porous MWNT yarn that allows liquid to escape easily. it can.

Such thread fuel cells have particular potential for application to small micro-airplanes such as dragonflies. Suppose you manufacture a braided tube that is braided (such as a shoe strap) and has a hollow, and you have a small MWNT thread of 30 microns or less that serves as a hydrogen electrode. This electrode is H on the surface of the braided structure⁺It is overcoated with a layer of electrolyte to be transported and wrapped around a sacrificial mandrel that makes the first layer of the fuselage or blades of a micro aircraft. The oxygen electrode thread (which does not require a hollow configuration) is then wrapped around the top of the hydrogen electrode, absorbing additional electrolyte and chemically treating it to remove the electrolyte only from the thread side on the surface of the aircraft. (As a result, three-point contact including air is ensured).

As an alternative to this type of configuration, fuel cell yarn structures with a diameter of 30 microns or less allow the electrolyte to be absorbed by the outer surface of the MWNT yarn with a diameter of 10 microns, and the electrolyte is still sufficient to provide partial infiltration on the side in contact with the electrolyte. It can be manufactured by twisting the hydrogen electrode MWNT yarn with a second yarn while it is wet. The hydrazine is then released into the hydrogen electrode thread to make the fuel cell operable (by using the released hydrazine as one fuel component and air as the second fuel component). Catalysts such as Pt or Pt alloys are of course useful for both fuel cell electrodes, and such catalysts can be easily deposited in the nanotube assembly in a region-selective manner using prior art methods.

Nanofiber stranded yarn wound on a spindle is particularly preferred for many of the above uses. This spindle may be one of the components of the final device, or it may be used in the arrangement of nanofiber strands and then removed in the next fabrication step.

(e) Sensor The nanotube twisted yarns of the embodiments of the invention have special utility as chemical and mechanical sensors that can optionally be woven or woven into fabrics. These nanotube threads can be incorporated into composite structures to detect mechanical deformation and damage occurrence events in these structures (before they result in catastrophic structural failure). Mechanical sensor applications can use changes in the electrical conductivity of the yarn that occur when the yarn is deformed, or blockage of electronic transport that occurs when the yarn breaks. For example, a twisted thread of nanotubes in a soldier's uniform provides an electrically transmittable signal that the soldier has been injured at a particular location, thereby enabling effective injured selection. Similarly, the toughness of the nanotube threads provides some protection against injury.

The application of chemical sensors in nanofiber strands can take advantage of electron transport and thermal power sensitivity by adsorption of chemicals on the nanofibers, as well as the reaction of chemicals or biological agents with derivatized or non-derivatized surfaces. The electrical conductivity and thermal power sensitivity of carbon nanotubes are well known (PG Collins, K. Bradley, M. Ishigami and A. Zettl, Science 287,1801 (2000) and J. Kong, etc., Science 287,622 (2000). )). The advantage of nanofiber yarns is that the mechanically robust structures incorporated into various structures, including chemical sensors in electronic fabrics, retain the high surface area of nanofibers.

Changes in the electrochemical capacitance of nanofibers in nanofiber yarns containing electrolytes are beneficially employed to provide response values for nanofiber yarn-based chemical sensors (including biochemical sensors). In the embodiment of the present invention, two nanofiber threads separated by an electrolyte are optionally adopted in the device configuration.

Examples 32 and 90 show how to make elastically deformable carbon nanotube sheets. These elastically deformable nanotube sheets are used as stress and strain sensors, and sensor responsiveness is provided by changes in the resistance of the nanotube sheets in response to the stress or strain applied. While the stress-strain sensitivity of the resistance value of the nanofiber sheet, which is strongly desired in most applications, is low, the magnitude of the elongation-induced resistance change is large enough to be useful for measurement. In addition, the magnitude of the stress-induced resistance change is the coating of the nanotube forest (for forest-based spinning) with a material that gives a large intrinsic resistance strain dependence (such as a properly selected conductive polymer). Alternatively, it can be enhanced either by coating or infiltration with such a material, or by the use of a device based on two nanotube sheets separated by a material that is highly strain dependent on the intrinsic resistance. In the latter case, the responsiveness of the sensor is determined by changes in the intrinsic resistance between the sheets (or the combination of intrinsic resistance between the sheets and within the sheet).

Piezoelectric and ferroelectric-based stress, strain or pyroelectric sensors can utilize the electrically conductive nanofiber sheets of the embodiments of the invention as electrodes on one or both sides of the piezoelectric or ferroelectric sheet.

The nanofiber sheet or sheet deposit used for one or both electrodes is thick enough to convert radiation into heat, as opposed to the pyroelectric sensor used to detect radiation (light or infrared radiation). You can choose to have. A large number of nanotube sheets can be stacked to obtain an appropriate electrode thickness for radiation absorption. These sheets are superposed to eliminate the effect of sheet anisotropy (eg, adjacent sheets are arranged orthogonally), or an arrangement of these sheets so that the orientation directions of the sheets are parallel. Can be overlaid with either. In the latter case, the pyroelectric device becomes sensitive to the polarization of adjacent sheets. A pixel-sensitive response is obtained for the pyroelectric radiation detector by using the method described in Section 10 (k).

Section 10 (k) details the use of carbon nanotube sheets and fabrics as sensors, and develops the electrical anisotropy of these sheets to obtain sensor responsiveness that allows them to monitor pixel arrays.

Numerous publications have been published on the use of nanotubes and nanofibers as sensors (see, eg, J. Li et al., Nano Letters 3,929 (2003) and J. Kong et al., Science 287,622 (2000)) and of this prior art. The teaching facilitates the application of embodiments of the present invention.

Instead of using the nanotube sheet of the embodiment as one or more electrodes to the piezoelectric sensor, the same type of device can operate in opposite directions as a piezoelectric or ferroelectric loudspeaker. One advantage over these tough nanotube sheets is that they are transparent and can be easily bent without loss of electrical conductivity. The use of these transparent nanotube sheets as electrodes on both sides of a piezoelectric or ferroelectric sheet allows the production of transparent loudspeaker window or pictorial coatings.

The method described in Section 10 (l) can optionally be used to embed the nanotube electrodes in the ferroelectric sheet material. In some cases, the polling process is performed after the embedding process.

Nanofiber electrodes for these sensors and loudspeaker applications are optionally densified, especially as densification increases the strength of the nanotube sheets.

(f) Incandescent light emitting device Although it is well known that carbon nanotube threads can be used as incandescent sources, prior art nanotube assemblies are untwisted (K. Jiang et al., Nature 419,801 (2002) and US Patent Application Publication No. 2004/0051432A1 (2004). March 18); see P. Li et al., Applied Physics Letters 82,1763-1765 (2003); and J. Wei et al., Applied Physics Letters 84,4867-4871 (2004)). The advantage of inserting twists to form the nanofiber yarns of the present invention is that the spinning process imparts mechanical robustness and the incandescent filaments to the extent that they can withstand repeated mechanical shocks without damage. To increase the lifespan.

The lack of significant strength and toughness loss due to knots and the low electrical resistance of the knots used to bind the separated nanofiber yarns together allow for adoption in this device and other device applications. It becomes.

In addition, due to the performance of carbon nanofiber yarns spun and twisted to withstand knots, which can be spun by the methods of the embodiments of the invention, and the very small yarn diameter (10 times smaller than the prior art yarns), the knots. Alternatively, incandescent light heating and localization of electron beam emissions in the region between knots are possible. The localization of incandescent light heating in knots can be beneficially employed to provide an incandescent light source with a diameter of less than a micron corresponding to the dimensions of the knots. Various methods can be employed to selectively increase the electrical resistance at the knot relative to the unknot region of the yarn (eg, selective chemical reaction at the knot).

Similarly, due to its mechanical durability and resistance to strength deterioration due to knotting, it is used in the production of nets and woven fabrics that function as incandescent light-heated structures.

Both multi-walled and single-walled carbon nanotubes serve as incandescent light sources. Unless the goal is to maximize the ratio of infrared light emission to visible and ultraviolet light, or to maximize lifetime, nanofiber incandescent lamps are 1500 ° C to increase electrical efficiency for photonic light emission. It is selectively preferable to operate with the above. If visible light emission is the goal, selectively preferably the nanotube-based incandescent light elements can operate at temperatures above 2000 ° C. If maximization of life is not always required, selectively preferably nanotube-based or other nanofiber-based incandescent elements are operated at temperatures above 3000 ° C.

These nanofiber-based incandescent sources are preferably those that surround the nanofiber incandescent element with an inert gas (such as argon, krypton, or xenon) or vacuum.

A second nanofiber can be added to the original nanofiber for the formation of incandescent light elements. Catalytic particles, such as metal or alloy particles, either before, during, or after the drawing process for producing nanotube threads, ribbons, or sheets for efficient incandescent or other applications. It is incorporated into (or on the surface) the volume of electrically conductive nanotube threads, ribbons, or sheets. Nanotubes from these catalytic particles (see references below) such that well-known CVD methods impart nanofibers (as well as field emitting nanofiber threads, sheets, or ribbons) containing elements for incandescent light. It can be used to grow from the original nanotube. It is selectively preferred that these nanofibers for the original yarn, sheet, or ribbon are carbon nanotubes.

Various changes can be made to these processes of adding secondary nanofibers to the primary nanofiber structure. They include (a) growth of nanofibers on pre-major or major sequences prior to formation of threads, sheets or ribbons, (b) second by solution-based infiltrated preform second nanofibers. These include the addition of nanofibers and (c) the creation of growth catalysts from the gas phase for the growth of second nanofibers.

Growing nanofibers inside or on the nanofiber yarns of the embodiments of the invention has broader uses than just for making incandescent or field emission elements. These methods include (a) mechanical reinforcement of nanofiber yarns, (b) enhancement of electrical or thermal conductivity of yarns, and (c) for example, other nanofiber yarns, other fibers, or matrix materials. It can be used for purposes such as providing nanofibers extending from the thread to electrically, thermally, or mechanically interconnect the thread with surrounding materials such as. These processes typically include (1) incorporating active catalyst particles into the nanotube yarn or precursor nanofiber array, and (2) catalysts introduced before, during, or after the twisting process on the yarn. It involves the step of synthesizing nanofibers in or on the surface of the nanofiber yarn by a reaction catalyzed by the particles. When the nanofiber yarn is incorporated into the fabric, this particle-catalyzed growth of the nanofiber inside or on the nanofiber is performed either before or after the yarn is incorporated into the fabric or other yarn arrangement. Can be done. This synthesis of nanofibers using catalytic particles may be CVD, liquid phase synthesis, or other known means. Useful methods of growing catalysts and carbon nanotubes include, for example, RGDing et al., Journal of Nanoscience and Nanotechnology 1,7 (2001); J. Liu et al., MRS Bulletin 29,244, (2004); and SMBachilo et al., Journal of American Chemical Society. 125,11186 (2003)). Catalysts and growth methods for other nanofibers are described below, see Y. Wu et al., Advanced Materials 13,1487 (2001); R. Tenne,

According to Example 29, a stable, planar light source of polarized UV, visible and infrared incandescent light (FIGS. 31, A and B) for sensors, infrared beacons, infrared images, and reference signals for device calibration. Is shown. The incandescent light of this nanotube sheet gives highly polarized radiation (as shown in Example 29), which has the advantage of giving an increase in the degree of polarization of the emitted radiation from 0.71 at 500 nm to 0.74 at 780 nm (Figure 32). It has, which is substantially higher than the previously reported degree of polarization (0.33 at 500-900 nm) for 600 μm long MWNT bundles with emission lengths up to 80 μm.

Reducing or eliminating the need for polarizers provides cost and efficiency benefits, and MWNT sheets provide spatially uniform emissions over a wide spectral range that would otherwise be difficult to achieve. The low heat capacity of these very small mass incandescent illuminants can be turned on and off within the time less than 0.1 ms they are observed in vacuum, and provides current-modulated illumination output on a shorter time scale. Will be done.

The polarized nature of the emitted light from the nanotube sheets (and other oriented electrically conductively oriented nanofiber sheets) can be used to reduce glare. For this purpose, the orientation of the nanofibers in the sheet is preferably at least substantially vertical.

The combination of electrical conductivity and transparency of the nanotubes to the sheet and ribbon also provides, for example, an electrically heated furnace and oven (the advantage here is high visibility to the heated contents of the furnace or oven). Is beneficially adopted for incandescent elements that should be transparent, such as). Similarly, the transparent nanotube sheet of the embodiment of the invention is almost invisible to the naked eye until it is electrically heated to generate incandescent light radiation.

The incandescent elements of the nanotube sheets of the embodiments of the present invention can optionally be superposed to increase filament strength. This superposition can optionally intersect the orientation direction of the sheet so that most of the in-plane mechanical anisotropy is removed. Such superposition can be used to convert the incandescent light of the nanotube sheet into a large amount of unpolarized light.

(g) Protective and temperature controllable garment applications The surprisingly high toughness illustrated by nanofiber yarns, as well as the extremely small yarn diameters, demonstrate the use of nanofiber twisted yarns as woven fabrics for protective clothing. Very dense yarn fabrics, such as those used for canvas, are particularly useful for resistance to punctures and punctures. The high temperature stability of drawn and plyed carbon nanotubes is particularly useful for producing hard armor that incorporates nanofiber yarns in a matric such as ceramics that are processed at high temperatures. Graphite fiber has high thermal stability, while the toughness (20 J / g or more) of the twisted yarn of the carbon nanofiber of the embodiment of the invention is higher than that of graphite (about 15 J / g).

The electrically conductive nanofiber yarns of the embodiments of the invention can be incorporated into the fabric to provide the ability to heat the fabric. Similarly, the electrically conductive nanofiber sheets of the embodiment of the invention can provide the ability to heat a woven fabric by being laminated between layers of a normal woven fabric and passing an electric current through the nanofiber sheets. These nanofiber threads and sheets are absorbent in the UV range, thus providing protection to the effects of solar radiation exposure to those who wear UV-transmissive clothing without it.

Another means of mitigating temperature changes in the fabric is to take advantage of the porosity of the nanofiber yarns and nanofiber sheets that store the phase change material, the heat of which melts absorbs thermal energy if the temperature gets too high. And when the fabric temperature is too low, it releases thermal energy. For use in garment fabrics, the temperature range of heat absorption and release is preferably selected within the wearer's comfort range.

(h) Applications as absorbent materials for gases, liquids and solids Due to the porosity, high surface area, small thread diameter, and high mechanical strength of the nanofiber threads, sheets, or ribbons of the invention embodiments, they are ideal for the concentration, separation, storage or release of gas and liquid components. Material. They are also useful as solids for concentration, separation, and storage, and can be collected in solid form, for example from vapors or liquids, and optionally afterwards vapors, liquids, liquid components, reaction products, solid forms, And a particulate solid or solid that can either be released or partially released in combination thereof. Such solids include, for example, biological agents such as bacteria and viruses, which can optionally be at least partially pyrolyzed or otherwise modified during the release process.

Carbon nanofibers, which are certain types of nanofibers, are useful in these applications. The weight surface area of the nanofibers for collection, separation, storage or release of these is selectively preferably 10 m.²/ g or more, selectively more preferably 100 m²It is more than / g. This surface area can optionally be measured using the well-known BET method.

The nanofiber assembly described above is particularly important for the concentration of the analyte present in gas and liquid, and subsequent heating, other means, or a combination thereof. Nanofiber assemblies made from yarns, sheets, ribbons, and combinations of these assembly methods are selectively preferred for material adsorption or absorption, material separation, and material release applications.

The high electrical conductivity of twisted yarns made of materials such as carbon nanofibers facilitates their use as materials for the separation, concentration and analysis of gas components. In a typical process using these conductive materials for this purpose, the threads, sheets, or ribbons of the carbon nanotubes absorb on the high surface area of the nanotubes. Exposure to the workpiece at a time that allows either separation or concentration by. This absorbed material can then be emitted by electrical heating of the nanofiber yarn, by absorption of radio frequencies or microwaves, or by absorption of irradiated ultraviolet, visible or infrared wavelength light.

Is the material (or components derivatized therein) collected on the nanofiber threads, ribbons, or sheets analyzed later, optionally, with respect to these articles using spectroscopic or other means? , Or released as a gas from these articles, and optionally analyzed by analysis of that gas. This gas can optionally be carried out using means such as mass spectrometer and gas chromatography. The material (or components derivatized therein) collected on the nanofiber threads, ribbons, or sheets can optionally be released into a liquid medium, followed by conventional liquid-based separation or analytical means. Used to separate or analyze.

Collection, separation, or release of solids, liquids, or gases from nanofibers (or components derivatized therein), including threads, ribbons, or sheets, eg, heating or capacity containing at least two electrodes. It is optionally electrically possible by capacitive charging to the means of the sex device. For example, in device means, capacitive charging can be performed by applying an electric potential between two electrically separated electrodes. Here at least one of these electrodes includes a sheet of nanofiber, ribbon, or thread (or a component derived from the same). Electrochemical charging can be effectively adopted by incorporating the electrolyte in the region between the electrodes.

Embodiments of these inventions are optionally reacted, surface derivatized, or surface coated to optimize the process of material uptake and material release of this portion. The coating may optionally include biological agents such as proteins, antibodies, DNA, aptamers.

Also, the pick-up and release of materials by nanofibers of this embodiment is optionally measured by ingestion measurements such as using surface acoustic wave devices or instruments, by measurement of electrical conductivity, or by measurement of thermal power. it can.

The materials used in the embodiments in this section are selectively preferred are nanofiber sheets, ribbons, and threads made in a solid phase process. The nanofibers are selectively preferably carbon nanotubes.

(i) Use as a channel for microfluidic circuits The porosity of nanofiber twisted yarn is useful as a channel for microfluidic circuits. These microfluidic circuits can be employed, for example, to create "fiber laboratories" for chemical and biochemical analysis on a centimeter scale or less, or more exclusively for chemical synthesis.

A new embodiment is to utilize the wicking performance of nanofiber strands for subsequent possible mixing and chemical reactions, separation (possibly along yarn length), and transport of chemicals for chemical analysis. ..

FIG. 13 shows an intersection that can be used as an intersection for microfluidic applications. This intersection consists of an overhand knot (1305) tied to one of the MWNT twins (with a fluid inlet along 1301 and a fluid outlet along 1302), where the knot is a second MWNT twin. Includes (fluid inlet along 1303 and fluid outlet along 1304). The nanofiber yarn in each of the twin yarns may be different in some cases, and in some cases the two twin yarns are different. Depending on the tightening of the inserted knots 1305, the different fluids that flow along 1301 and 1303 may mix to produce different fluid mixtures and flow out along 1302 and 1304. As the knot tightening increases, the fluid component flowing in at 1301 increases the outflow along 1304 and the fluid component flowing in along 1303 increases the outflow along 1302. The transport of fluid along these yarns is optionally when the single yarns of the components within each twin yarn are electrically insulated from each other and these yarns are electrically conductive. It can be modified by applying an alternating or constant potential between the inlet and outlet of the twin yarns and between the single yarns of the components in each twin yarn.

These and many other types of thread-based microfluidic circuits can optionally be arranged on curved or straight surfaces to produce the final device configuration. Optionally, as another preferred configuration, these microfluidic threads can be formed in woven, sewn, embroidered, or other configurations in the fabric. To ensure that microfluidic circuits are defined, the other thread or fiber portions are substantially selected (or modified), for example, of their hydrophobicity / hydrophilicity and / or porosity. It can be manufactured so as not to interact with the microfluidic circuit. These yarn-based microfluidic circuits can optionally include one or more fabric layers, and the microfluidic yarns in one fabric layer can optionally traverse between the fabric layers. Similarly, a microfluidic nanofiber yarn structure (such as a yarn in a composite) optionally provides mechanical reinforcement of the composite structure. In addition, optionally, the nanofiber yarn may contain materials known in the art that mechanically reinforce the structure at the onset of yarn breakage.

For textiles in garments that analyze biological products for health monitoring purposes, such microfluidic circuits can optionally be used for a variety of purposes. Similarly, microfluidic mixtures (as illustrated in FIG. 13) can be used for mixing fuels and oxidizers for small fuel cells and combustion engines that can be used in small robots or micro-aircraft.

(j) Tissue scaffolding and other biological uses The spun yarns and sheets of the embodiments of the invention can also be used as scaffolds for tissue growth in either organisms or cultures, including humans. Available examples include the use of nanotube threads as a scaffold for neuronal proliferation after brain or spinal cord injury. Recent studies have shown that functional neurons proliferate quickly from carbon nanotubes, and carbon fibers less than about 100 nm in diameter slow scar growth and promote the growth of desired cells (H. Hu). , Y.Ni, V.Montana, RCHaddon, V.Parpura, Nano Letters 4,507 (2004); JLMcKenzie et al., Biomaterials 25,1309 (2004); and MP Mattson et al., J. of Molecular Neuroscience See 14,175 (2000)). For the purpose of modifying biocompatibility, spun yarns and spun nanotubes in sheets are optionally due to, for example, DNA, polypeptides, aptoma, other polymers, or special growth factors such as 4-hydroxynonenal. It can be chemically derivatized by wrapping or the like, or non-chemically derivatized. The carbon nanotube threads and sheets of the embodiment of the invention, which can be produced without any additives (although the selected additives can be incorporated and the nanotube threads can be derivatized if desired), are electrically conductive. Is expensive and very durable. Similarly, unlike other high-performance fibers / yarns (such as Kevlar® and Spectra® fibers used in bulletproof vests), these toughness yarns have advantages for medical applications. It is highly resistant to strength deterioration due to either wear and has substantially controllable elasticity. These threads can be woven into two-dimensional or three-dimensional fabrics that can act as a skeleton for the growth of blood vessels and nerves. The woven fabric can have virtually any desired shape: we have produced tubular structures from nanotube yarns and from wraps of spinning ribbons with moderately small vessel diameters (implemented). Example 11). The nanofiber threads of the embodiments of the invention can be used as electrical connections to neurons in the brain, ear (for sound detection), or eye (for light detection), where functional neurons are electrically connected to existing neurons. It is propagated on nanofiber threads to connect. Neuronal proliferation on the tips of nanofiber threads with diameters smaller than 10 μm is selectively preferred to be used for these applications.

One major problem in using scaffolds for tissue growth is to ensure proper elasticity of the scaffold both during tissue growth and after such growth has been largely performed. The situation is similar to that of a fracture-it is desirable to stay stationary while the treatment is in progress, but it is desirable to restore normal mobility and elasticity after the treatment process has progressed sufficiently. When the initial scaffold material is impregnated with a host material (such as a relatively rigid bioabsorbable polymer), the nanofiber twisted yarn imparts this elastic synchrony and its bioregulated absorption makes the nanofiber yarn normal. It is opened to have elasticity with good physical function and mobility.

Nanotube yarns have electrical conductivity, mechanical strength, flexibility, and chemical stability, so they are, for example, in inductor coils for implantable sensors and implantable radio transmitters and transponders. It can be used for various implantable biomedical devices. Prior arts that use carbon nanotubes as biochemical sensors are well developed, as illustrated by the selectivity of nanotube sensors and the research methods for obtaining selectivity. Since it is also well known that functional neurons proliferate easily on carbon nanotubes, carbon nanotube threads and sheets could be used as highly efficient electronic interfaces to axons. The advantages of using carbon nanotube threads and sheets for these applications, as opposed to other types of nanotube sheets and threads, are the enormous surface area available, high mechanical strength, high electrical conductivity, and the required bonding. The combination is the absence of the agent and the resulting thread diameter and small sheet thickness.

For some types of nanofiber synthesis and processing methods, the result is an undesired tendency for blood to clot on the nanofibers and nanofiber assemblies, but with different materials to prevent clot formation. It is useful to coat the nanofibers. One of the useful materials that can be used to prevent or reduce the formation of blood clots is amorphous carbon. Other useful materials are proteins known in the prior art.

(k) Applications of nanofiber sheets and textiles for addressing individual elements in 2D and 3D arrays The surprisingly high electrical anisotropy that we have noticed for the electrical conductivity of nanotube sheets is utilized in addressing selected regions (or pixels) of these sheets in a two-dimensional or three-dimensional array. Provides another type of embodiment of the invention. According to Example 23, this electrical anisotropy ranges from a medium value of 10-20 typical for densified carbon nanotube sheets to a high value of about 50-70 for non-densified sheets. Appropriately pre-drawn perpendicular to the drawing direction to increase the anisotropy of electrical conductivity of the densified or non-densified carbon nanotube sheets, varying to any high value. Will be done.

In one type of such embodiment, these two highly anisotropic sheets were placed parallel with orientation between the highly conductive directions in these Θ sheets. This angle between the orientation directions of the two sheets is optionally between about 30 ° and 90 °, preferably about 90 °. These sheets are separated by one or more coatings or layers that give the current path along the nanotube sheet a higher effective resistance between the nanotube sheets, which is the main reason why the current path in the sheet is widened. This is due to the deviation of the anisotropy from the infinity.

Means for selectively applying a voltage at any position (pixels) in the material separating the nanotube sheets is provided by the attachment of electrical contacts along at least one face side of each sheet. These contacts are preferably separated by a linear arrangement that is at least substantially orthogonal to the orientation direction of the nanotubes in each sheet. The distance between electrical contacts on the lateral sheet surface is measured by the distance of the components orthogonal to the orientation.

This means for selectively addressing different pixels can be used to selectively address elements for a variety of purposes, depending on the nature of the resistant material that separates the nanotubes.

The material that separates the two nanotube sheets in these different pixels depends on (1) mechanical stress (eg, piezoelectric material, piezoelectric or polled ferroelectric, stress and strain within the pixel). A light detector for (eg, a dielectric that imparts capacitance between charged sheets), (2) local temperature, (3) localized visible light, infrared-irradiated ultraviolet rays, or high-energy gamma-ray or particle-irradiated light. , Based on photoinduced conductivity, heat-induced resistance changes to the material between the nanotubes), or (4) pixels between sheets that respond to liquid or gaseous materials, especially biological materials. It may be a sensor material for an artificial nose (for gas sensing) or an artificial tongue (for liquid sensing) using a region material. It should be noted that the material of (1) can be used to provide computer screens and electronic fabrics that allow the input of data by utilizing the change in electrical conductivity caused by contact or the sensing of electrical signals.

The material that separates the nanotube sheets in the pixel region may be a material or material assembly that either directly or indirectly causes light emission or color change depending on the voltage applied to the pixel. Visible, infrared, and / or infrared wavelength light emission in a pixel can be achieved by a variety of means, including fluorescence, phosphorescence, or incandescent light. For example, the material that separates the pixel areas of the nanotube sheet may be the material or material assembly used in the prior art for light emitting displays. Alternatively, the material that separates the pixel regions of the two nanotube sheets may be a resistant material that emits incandescent light (or incandescent light that predominates only in the infrared region as a result of low temperature heating). Emission of infrared light by means of fluorescence or incandescent light can be used to help reduce the visibility of background items for military applications.

In other useful embodiments, the high resistance material or material assembly between the pixels of the two nanotube sheets may be those that provide color change. Examples are those that provide a color change as a result of heating (such as thermochromic organic polymers, thermochromic inorganic materials, or thermochromic liquid crystals), electrochromic materials (such as liquid crystals), or electrochemical materials (such as second). An electrochemically switchable conductive polymer comprising an electrode attached to a first nanotube separated by an electrolyte from a counter electrode attached to an nanotube sheet).

Responsive layers or coatings between the sheets can be applied by various means, such as coating individual nanotube sheets with one or more layers prior to laminating the nanotube sheets. The material deposited as a resistant material uses the method used to manufacture the elements of combinatorial chemistry and is spatially gradiented between sheets by sheet-to-sheet deposition or by deposition of multiple materials. It can be changed by passing the area between them. These methods are especially useful for manufacturing smart noses or smart tongs.

The space between two orthogonal sheets containing oriented nanotubes can also be effectively separated by air, other gases, or vacuum. A novel matrix addressing using air, other gas, or vacuum is illustrated in Example 54.

Two or more nanotube sheets (or deposits of nanotubes in direct contact) are images to three-dimensional pixels when the responsive material layer separates adjacent nanotube sheets (or deposits of adjacent nanotube sheets). Can be used for disassembly. Each nanotube layer (or deposit, or identically oriented nanotube sheet) is then the same as if only two sheet layers were present (or contact deposits of identically oriented nanotube sheet deposits). Can be addressed independently.

The method of these embodiments is that adjacent non-electrically contacted nanotube sheets are electrically located within or between sheets (outside the region where the responsive or responsive material assembly is located). The same applies when replaced by two fabric sheets containing insulated carbon nanotubes. The responsive material between the woven layers is provided by coating a layer of responsive or responsive material on top of the yarn before or after the assembly of the nanotube yarns is made into a woven fabric. If the nanofiber yarns in the fabric layer are in more than one direction inside a given fabric layer, these yarns in different directions are not due to mutual contact due to the arrangement of resistant responsive materials or responsive materials. Should be substantially electrically isolated from each other.

These methods work by arranging the nanofiber yarns in two directions to prevent direct contact, or by insulating all the yarns in the fabric with a cover to achieve image decomposition into the desired pixels. Also applicable to a single woven sheet. The lowest resistance contact between adjacent threads depends on the electrically responsive material or material assembly. In such cases, the pixel-image-resolved response is given by the individual addressing of the individual nanotube threads in the fabric.

Such electrically anisotrophic sheets and fabrics are permanently either the applied voltage (such as liquid crystal), the voltage-driven current flow (such as the electrochemical switch of conductive polymer), or a combination thereof. It can be used in information storage devices by utilizing a resistant responsive element that is subject to either a target or reversible intrinsic resistance or a change in capacitance. For permanent storage of information, the responsive element is simple and may be an element that evaporates (opens the circuit) or carbonizes (closes the circuit) as a result of the pixels being addressed.

Instead, either permanent or reversible memory and retrieval of information (or permanent recording with local radiation exposure), radiation (such as light) and reading of this information, and / or the above sheets, textiles, Alternatively, it can optionally be obtained by writing and / or deleting information using pixel response switching in the opposite direction using the pixel addressing capability of a combination of sheet and textile arrangements.

These methods are applicable to electrically conductive nanofiber threads and electrically anisotropic nanofiber sheets, which optionally contain no carbon nanotubes or contain carbon nanotubes in combination with other nanofibers.

(l) Welding of meltable materials and surface modifications using selective nanofiber heating and electrical heating at frequencies in the microwave, radio frequency, ultraviolet, visible and infrared regions.

Example 30 shows polymer welding by heating a transparent MWNT sheet sandwiched between plastic parts. The MWNT sheet strongly absorbs microwave radiation, as evidenced by its use in welding plastic parts in microwave ovens. In this example, the MWNT sheets are sandwiched between two 5 mm thick Plexiglas® plates, welded tightly to each other using heating, and are durable, preserving nanotube orientation and electrical conductivity. A uniform, highly transparent interface is provided. Microwave heating was performed in a 1.2KW microwave oven operating at 2.45GHz. Figure 33 shows two 5 mm thick plexiglass (potimethyl methacrylate) plates, with two 5 mm thick plexiglass (potimethyl methacrylate) plates welded to each other using MWNT sandwiched sheets using microwave heating. A tough, uniform, transparent interface was obtained with little change in the orientation of the nanotubes and the electrical conductivity of the sheet. The combination of high transparency and superthermal stability offers advantages not found in previously used conductive polymers for microwave-based welding. Among other applications, this microwave heating process uses polymer composites from polymer sheet deposits separated by nanotube sheets, electrically heated car windows, and antennas in car windows with high transparency. Can be used to manufacture.

Welding of contacted meltable materials by selective heating of nanofiber sheets is performed in nanofibers at radio frequency, infrared frequency, visible light frequency, infrared frequency, ultraviolet frequency, and combinations thereof, and in combination with microwave heating. The same can be done by using the selective absorbency of the sheet. Also, the selective heating of the nanofiber sheet for welding the nanofibers with the meltable material can be performed by electrical contact heating of the nanofiber sheet. The intensity and duration of the radiation-induced or electrically-induced heating process should be sufficient for at least partial melting of the meltable material in contact with the nanofibers. The intensity of the radiation and the electrical output delivered by electrical contact heating are preferably high enough for the liquefaction of the meltable material to occur locally only in the area of contact with the nanofiber sheet. The degree of region-selective irradiation or region-selective electrical contact heating to the nanofiber sheet, or a combination thereof, and the degree of welding with a meltable material or multiple materials can be determined by any area selection method. Can be set.

There are few restrictions on the selection of meltable materials for these processes. However, it is preferable that the meltable material has a sufficiently low viscosity at the melting temperature and flows at the desired time scale required for rapid processing. When the molten material is an organic polymer, the upper limit of the melting temperature is usually constrained by the deterioration temperature of the polymer. However, the meltable material for the welding process is preferably one that does not have significant absorption at the wavelengths used for heating. If the heating process is by electrical contact with the nanofiber sheet, the meltable material should be substantially electrically insulating.

Molten polymers of polycarbonate, polyvinyl butyral (eg, commercially available under the trade name Salflex®), polymethylmethacrylate, and polystyrene are particularly preferred for the interlayer welding process described above and the surface welds described below. .. Similarly, inorganic and organic glasses are preferred.

In the case of welding using polyvinyl butyral, selectively preferably this polymer is sandwiched between the flat surfaces of the glass. For processing using radiation-induced heating of polyvinyl butyral, glass / polyvinyl butyral / nanofiber / glass overlay or glass / nanofiber sheet / polyvinyl butyral / nanofiber sheet / glass overlay is another means. It is preferably heated by microwaves.

The above-mentioned electric heating means and the heating means by absorbing radiation are a sheet of molten polymer and a molten woven fabric (or a molten sheet including a molten woven fabric) in an overlapping region of these threads and woven fabrics on which the nanofiber sheet of the embodiment is arranged. Can be used to weld the layers together.

The nanofiber sheet can be conveniently applied in a manner related to the surface of plastic or other meltable material, and only the low melting point polymer melts as a result of the temperature rise caused by the radiative absorption or electrical contact heating of the nanofiber sheet. A nanofiber sheet can be attached between the low melting point polymer and the high melting point polymer selected in the above manner.

These surface and interlayer bonding methods allow the incorporation of nanofiber-based antennas and heating elements, such as window layers, either in the surface area of the meltable material or between layers of the meltable material.

Other advantages of such a surface bonding process are the enhancement of desirable mechanical properties for the surface area and the electrical conductivity provided by the nanofiber sheet. The surface energy of the surface area incorporating the nanofibers depends on the degree of heating caused by the infiltration of the nanofiber sheets.

If the degree of infiltration of the nanofiber surface area is incomplete, then the carbon nanofibers will protrude from the surface and the surface treatment process will result in a highly hydrophobic surface. Such a highly hydrophobic surface is effective in avoiding the condensation of water droplets, and can be adopted for avoiding fogging of optical elements.

The surface energy and the degree of hydrophobicity accordingly are affected by the gas absorbed. This dependence can be eliminated and the surface is of a nanofiber or bundle of nanofibers whose surface intentionally projects a hydrophilic or hydrophobic material (or a material with a mixed nature of hydrophobicity and hydrophilicity) from the substrate. It can be either hydrophobic or hydrophilic by being absorbed above.

In addition, two parallel, non-contact nanofiber sheets were placed in the surface area so that one of these sheets was completely embedded and separated from the surface nanofiber sheet by an ionic conductive layer. The surface can be reversibly adjusted electrically between hydrophobic and hydrophilic. The application of an electric potential between the two nanofiber sheets results in an electrochemical charge of the nanofiber sheets, resulting in a change corresponding to the surface energy of the sheet, which determines the wettability. Obtaining an adjustable charge A suitable assembly for this purpose to be wet is to attach a nanofiber sheet on the surface of the molten material (or if the surface material does not have useful meltability). Can be placed and layered on top of this nanotube with a meltable solid electrolyte and the next nanofiber sheet (where it becomes the outer surface layer). By compressing this deposit with another material (which does not cause unwanted absorption of chemical beam radiation used for melting or radiation-based nanofiber heating or electrical conductivity that interferes with electrical contact-based welding). When applied to cause melting by radiation of chemical rays or heating of electrical contact, it is possible to fabricate two electrode outer layers separated by the target electrolyte.

(m) Substrate for patterned deposition of oriented nanofibers-utilization of supporting nanofiber sheets Applicants have patterned a layer of oriented nanofibers with a local mechanical stress of 30 nm or less, retaining the nanofiber orientation from one substrate (moving substrate) to another (receiving substrate). It was found that it can be transferred as a sequence.

For example, according to Example 34 and FIG. 37, substrate-supported carbon nanotubes with carbon nanotubes 30 to 50 nm thick on a substrate are mechanical to produce transfer images with approximately the same thickness on another substrate. It is shown that it can be transferred. This transfer occurs without substantial loss of nanotube orientation. When a substrate-supported nanofiber sheet is placed face down on standard writing paper and written on a non-porous support paper with a sharp object, the nanotube sheet changes from the surface of the non-porous paper to a stationary paper. It was transferred. The left figure of FIG. 37 shows the nanotube sheet attached to the substrate (non-porous paper) after transfer, and the right figure shows the normal writing paper having the transferred image.

Most importantly, light microscopy of the transferred nanotube sheet area preserves the arrangement of nanotubes on the original nanotube-coated sheet in the nanotube pattern transferred to the porous paper. Is to be shown. Therefore, the orientation of the nanotubes in the transferred circuit pattern can be freely controlled by changing the relative orientation between the sheet that produces the image (the substrate to be transferred) and the sheet that receives the image (the receiving substrate).

In the results of FIG. 37, the nanofiber sheet is densified by the liquid treatment densification method of Example 23 prior to the nanotube transfer step. Other results in Example 34 show that non-densified nanotube sheets can also be used to transfer patterned sequences of non-densified oriented nanofibers. This method is less attractive than the one using a densified sheet. This is because the nanotubes transferred to a part of the porous paper are not under the writing instrument. Nevertheless, the transferred nanotube sheets are bound more tightly than those accidentally transferred to porous paper, and the latter can easily dispel intentionally transferred nanotubes without disturbing them.

This process has general applicability for nanofiber sheets oriented with respect to the nanofiber orientation. These results indicate that both densified and non-density nanofiber sheets can be used for deposited patterned arrays of oriented nanofibers.

Instead of using the stress applied locally to provide the deposition of patterned nanotubes from the nanotube sheet to another substrate (the receiving substrate), the receiving substrate is patterned (by lithography or mechanical means, etc.) and rises. It can have surface areas that have been and have been lowered. Uniform stressing of the transfer sheet or other substrate can then be used to receive the nanotubes and transfer them to the elevated region of the substrate.

In another embodiment of the invention, selective area transfer of nanotubes from the transfer substrate to the receiving substrate (ie, patterned transfer) is a pattern of a meltable material (such as a polymer) on the receiving substrate. This can be achieved by depositing sequences. The transfer substrate is in contact with the receiving substrate, followed by heating to the melting point, and then cooling to transfer the nanotubes from the transfer substrate to the receiving substrate. This heating can optionally be achieved by microwave or high frequency heating of the nanotube sheet.

Such a patterned array of oriented and deposited nanofibers can be used in the fabrication of nanofiber circuit elements such as, for example, electronic wires and internal connections, antennas, resistors, capacitors and supercapacitors.

Similarly, the transfer of such nanotubes from the transfer substrate to the receiving substrate can be repeated one or more times, as in the case of increasing the thickness of the deposited nanotubes in a selected area. Similarly, additional transfer, a process between transfer and receiving substrate, can be used to reduce all parts of the anisotropy of the area of the transferred material. For example, this can be done by changing the orientation of the transfer and receiving substrate during the subsequent transfer process. In addition, the first deposition process is with another material, such as a film-like supercapacitor or a solid-state electrolyte for a dielectric for ordinary capacitors, of the entire receiving substrate (or some part of it). Subsequent in the coating process. This second coating process is then followed by an additional transfer of nanotubes from the transfer substrate (or second transfer substrate) onto the material provided by the second coating process. Such a method can be freely repeated to unfold the multilayer structure.

(n) Nanofiber sheet applique Example 31 shows that a transparent carbon nanotube sheet can be coated with a film adhesive as an electrically conductive layer that provides the electrical conductivity required for microwave absorption and resistance heating. In addition, according to this embodiment, the adhesive on the adhesive film can be extruded through the nanotube sheet to provide a high degree of adhesion to the metal, glass, plastic, and other surfaces of the laminated adhesive film / nanotube sheet. Is shown. When attached to a flexible substrate (such as a polymer), this example (and FIG. 34) allows the tape / nanotube sheet / plastic sheet to reach high angles without causing significant changes in the in-plane resistance of the nanotube sheet. It is shown that it can be bent repeatedly.

Example 42 describes an apparatus for manufacturing an nanotube sheet to be attached to an adhesive tape. Examples 50, 51, and 52 show means for storing the grown nanotube sheets, which can be used for subsequent attachment of the nanotube sheets to the adhesive sheet.

(o) Nanofiber sheet filter Achieving high filtration rates at the same time with the ability to filter very small particles such as viruses, bacteria, and colloidal particles on the nanometer scale is usually difficult for both gas and liquid filtration. is there. Especially when the filter is thick, it is a problem that a low filtration rate is given by a small pore size. The filtration rate can be increased by reducing the filter thickness, but on the other hand, if the filter thickness is small, the filter may burst, so the pressure difference on the opposite side of the filter must be reduced. It partially eliminates the filtration rate advantage of using a thin filter membrane.

The nanofiber sheet extracted in the solid state of the embodiment of the invention solves this problem by providing a strong filtration membrane in which rupture of the filter membrane is not so problematic even if the nanofiber filter is very thin. Helps solve.

According to an embodiment of the present invention, a filter structure comprising a solid-state extracted nanofiber sheet or sheet laminate having a small pore size attached in at least one size by a thicker film having a larger pore size. Is provided. The average pores of the thicker membrane are chosen to be at least twice as small in maximum dimensions as typical nanofiber lengths.

If the nanofiber sheets are highly oriented, in some cases two or more sheets can be stacked across the nanofiber orientation directions, resulting in a low lateral strength orthogonal to the orientation direction in one sheet. It is reinforced by the high strength of the laminated sheets in the orientation direction.

The significantly increased effective loading capacity of the nanofiber membrane is preferably due to the nanotubes that cross the contacting pores in the supporting fileter structure. The advantage of this arrangement is that the resistance to filter rupture is determined by the strength of the individual nanofibers, which is generally much higher than that of the sheet. Therefore, the advantage of filtration rate by using a very thin sheet thickness can be realized without risk of membrane rupture even when a high pressure drop is applied to the entire filtration membrane.

The porous material that supports the nanofiber sheet membrane should be on the low pressure side of this membrane and, optionally, can be chosen to trap larger size particles. Due to the cleaning of the membrane by applying a pressure difference in the opposite direction over the entire membrane, the membrane of the nanofiber sheet can optionally be supported on both sides by a thinner membrane with a smaller pore size.

The support membrane or membrane with a larger pore size may be any type of various conventional membranes and may optionally include fibers or nanofibers. Alternatively, the support membrane can be a sheet material with holes or channels, such as, for example, a metal wire grid, a metal plate with holes, or an anodized aluminum sheet.

Nanofiber membranes preferably contain carbon nanotubes, and at least one of these potential membrane deposits is involved in solid state assembly (eg, the process of Examples 21, 50, and 52). It is preferably assembled by the processing steps of the present invention. Sheets made in the solid state are preferably densified by a liquid-based densification process such as in Example 23. However, nanofiber sheets may optionally include non-density nanofiber sheets, especially for gas filtration purposes such as air filtration.

Of course, embodiments of the present invention apply to both planar and non-planar filters. A particularly preferred non-planar filter is a columnar or conical film. Similarly, nanofiber-based membranes can be suitably used for cross-flow filtration, which minimizes filter clogging by allowing the liquid to be filtered to pass tangentially to the fileter membrane.

(p) Additional applications of nanofiber sheets and ribbons as transparent conductors Carbon nanotube sheets (and ribbons) extracted in the solid state have a wide range of uses as transparent conductors, and in some cases, the strength, toughness, microwave absorption performance, polarization emission and polarization of nanofiber sheets. It is facilitated by absorption performance, adjustable work function, extreme flexibility without degradation of electrical and thermal conductivity, and porosity of the nanotube sheet.

Some of these are applications described in Examples: Example 14, for transparent substrates and electrodes capable of optically monitoring cell proliferation, low noise, low electrical conductivity, low temperature dependence transparent sensors 25, a transparent light source of polarized incandescent light, 29, a transparent conductive layer (electromagnetic wave shield, antenna, and heating) coupled with microwaves for a transport layer for microwave welding of plastics. 30 for elements), 31 for transparent appliques, 32 for transparent elastomer electrodes, 33 for transparent organic light emitting diodes, and 34 for transparent printed circuit elements.

Coupled with electrical conductivity, transparency is also useful for producing transparent, low-visibility supercapacitors that are conformal to the surface, such as flat sheet supercapacitors. Such a transparent, low-visibility supercapacitor preferably contains two nanotube sheets separated by an electrolyte.

Sheet transparency is also useful for the use of carbon nanotube sheets and ribbons for electromagnetic (EMI) shielding. For example, transparent nanotube sheets can be used to provide EMI shielding to optical displays such as computer screens.

Also, transparent nanotube ribbons and opaque nanofiber ribbons (possibly spirally wound) can be used for the outer cover of coaxial wires and cable electromagnetic shields, where signals or power are applied to the inner regions of the cables. The transport component is included and the nanotube EMI cover is separated from this inner signal or power transport component by an electrical insulating layer. These types of electromagnetically shielded wires are particularly useful for applications in electronic fabrics, where they provide a combination of low visibility and structural reinforcement of coaxial wires.

The combination of electrical conductivity and transparency of nanotubes to sheets and ribbons is also beneficially adopted for transparent heating elements. These heating elements are used in electronic fabrics for clothing, in windows of automobiles and aircraft, and in electric heating furnaces or ovens (where the advantage is that they provide high visibility into the heated contents of the furnace or oven. Yes) Can be adopted. Substrates are useful and are optionally employed in such transparent electric heaters or ovens, said substrates are optionally glass or quartz substrates.

Light emitted from the heating elements of a hot oven obscures the visibility of the contents of the oven. This problem is mitigated by taking advantage of the polarization characteristics of the emitted light from the heating elements of the sheet or thread of the oriented nanotubes (see Example 29). Visibility of the contents of the furnace can be improved by placing a polarizing sheet or a material having reflectance depending on the reflectance between the observer and the incandescent nanotube emitter. The preferred direction of light absorption or reflection is optionally parallel to the primary polarization direction of the emitted light from the heating element of the nanotube sheet, which is parallel to the orientation direction of the nanotubes. The efficiency of the oven or furnace is increased by using a polarizing element that polarizes by reflection that returns light and infrared radiation into the oven or furnace by means that are largely non-absorbent.

A transparent carbon nanotube sheet or ribbon coating on windows, eyeglasses, and similar devices (such as binoculars) is optionally oriented so that the polarization effect of the nanotube sheet minimizes glare. This can be done by orienting the nanotubes on the nanotube sheet so that they are aligned at least substantially horizontally.

The use of transparent nanofiber sheets as one or more electrodes for displays such as newspapers and other related displays is also important, and in such applications the nanotube sheets of the embodiments of the invention provide conductivity and It provides the advantage of flexibility with no loss of transparency. A potential substrate for such a one-sheet newspaper could optionally be a sheet material such as regular newspapers (or materials with similar properties), and updates to these pages are transmitted wirelessly. May be possible based on currently available information.

The color changes used for these newspapers are changes in nanofiber sheet electrodes in newspapers, color changes due to liquid crystal base, color changes due to thermal drive of thermochromic materials, color changes due to electron wet drive, and one of the electrodes. Electrochemical color change of the components in the individual (including contact with electrochromic nanoparticles or nanofiber electrodes with electrochromic coating), electrodes between electrodes that give color change Particles between electrodes that rotate in response to an electric field, electrodes This is possible by particles between the electrodes rising or falling to impart the required color change in response to the mutual electric field, or by other means known in the art. Examples of the use of electronic wetting for electronic paper displays are given by RA Hayes and BJ Feenstra, Nature 425,383 (2003).

The chromatic display of the embodiment of the invention may be the first substrate on which it is electrically conductive, white, near-white, or appropriately colored, either directly or indirectly. A transparent second electrode attached to the electrode of the device and a material or material system that provides either direct or indirect electrically driven chromatic responsiveness can be included, at least one of the transparent electrodes being nanofibers. It is an electrode. In some cases, the nanofiber electrode is preferably an nanotube containing the electrode.

Nanofiber electrodes in such as electronic newspapers and chromatic displays can optionally be composed of nanofiber sheets, ribbons, threads, fabrics, and non-woven fabrics. These electrodes optionally provide primary mechanical support for displays such as electronic newspapers, or these electrodes can be layers supported by another material or material assembly.

The details of transmitting information to the newspaper (generally by wireless communication) are not the subject of the present invention and the means are known in the art. However, we hereby illustrate the properties of the electrodes of transparent nanofiber sheets that are beneficially employed in such electronic newspapers.

These electrically conductive and transparent nanofiber sheets are described in textbooks, such as U.Back et al., Advanced Materials 14,845 (2002), and are electrochemically provided with prior art brittle metal oxide sheets. Can be replaced. These transparent, electrically conductive sheets can also replace the electrodes used in the adjustable wet-based displays described in RA Hayes and BJ Feenstra, Nature 425,383 (2003).

Example 52 describes means by which nanofiber sheets can be attached to cellulose-based papers and sheets, and these methods generally apply to embodiments of these inventions.

(q) Elastically deformable nanofiber sheet Examples 32 and 90 illustrate how transparent carbon nanotube sheets can be transformed into highly elastic and deformable electrodes. And it can be used as an electrode for high strain artificial muscles, to convert high strain mechanical deformations into electrical energy, and to make large amplitude vibrations adjustable damping. An exemplary material for actuators is silicone rubber.

These elastic nanotube sheets vary by more than 100% in dimension while maintaining a substantially in-planar resistance value. As shown in FIG. 35, the initial sheet resistance of the silicone rubber / MWNT sheet composite obtained without load was 755 Ω / square. However, after the initial increase of resistance ~ 6%, the resistance changed less than 3% during the subsequent 4 strain cycles up to 100% strain.

Ordinary conductors cannot undergo such large strains without losing electrical contact with the working material. Conductive greases are used to maintain electrical contact with electrostraining materials that generate 100% or more strain (R. Pelrine, R. Kornbluh, Q. Pei, and J. Joseph, Science 287, 836). (2000)) On the other hand, these greases are not suitable as electrodes for electrostrained sheet deposits that can generate large forces and high strains without the need for an applied potential of thousands of volts.

Further experiments (see Example 32) show the general use of this method of providing highly elastic electrodes on a woven substrate that can be elastically stretched. For example, the attachment of a 120% stretched elastic spandex® fabric of a non-densified nanotube sheet (adjusted in Example 22) (by pressing, then application of the liquid-based densification process of Example 23). ) The result is an nanotube electrode material that can be elastically relaxed and repeatedly re-elongated to the initial elongation without undergoing a substantial resistance change. Suitable spandex (registered trademark) fibers and / or textiles are made by DuPont (and called Lycra® fiber and Sandura® fabric), Dorlastan Fiber LLC, INVESTA, and Radici Spandex Corporation.

For applications that require a large range of elastic deformation of the nanofiber sheet or ribbon, the elongation of the elastic sheet prior to nanofiber deposition is preferably at least 4%, more preferably at least 10%, and most. It is preferably at least 100%.

Elastic Deformability Woven fabrics suitable as elastically deformable material substrates for nanotube sheets are those that are highly elastically deformable in one direction in the plane (such as Spandex®), and Examples include those that are highly elastically deformable in two directions in a plane (such as a blend of Lycra® and Nylon®, Tru-Stretch® ). Differences between these different elastically deformable fabrics are well known in the art and are largely due to the way these fabrics are woven and / or the chemical formulation of the fiber or yarn components. ..

Methods of converting less elastically deformable sheets and ribbons to highly elastically deformable sheets and ribbons can be performed on a variety of sheets and ribbons, including many different types of nanofibers and nanoribbons. , Some of which are described in Section 2. These nanofibers and ribbons are selectively preferably having a length of about 10 microns or more, and selectively more preferably 100 microns or more. Similarly, the ratio of the length of the nanofiber or nanoribbon to the thickness of the nanofiber or nanoribbon at the thickest side dimension is selectively preferably 100 or greater, selectively more preferably 1000 or greater, and selectively most. It is preferably 10,000 or more.

This described method of making a nanofiber sheet or ribbon elastically deformable by attaching the nanofibers to an elastically stretched substrate is a method of nanofibers with little or no in-plane alignment of nanotubes and It can also be used for nanofiber sheets.

Similarly, the initial elongation of an elastically deformable (or pseudo-elastically deformable) substrate can be biaxial elongation.

In addition to being applicable to porous elastic fabrics (Example 32), these methods for making nanofiber sheets and ribbons elastically deformable include porous elastic sheets (such as porous silicone rubber sheets). ) Can be executed.

The nanofibers can optionally be formed as a sheet on a pre-stretched porous elastic sheet directly by filtration of the nanofibers dispersed in solution or in a supercritical fluid. In such a process, the pre-stretched porous sheet optionally acts as a filter for nanofiber deposits. In such cases, known methods of forming aligned or unaligned nanofibers as sheets can optionally be employed.

Suitable nanofiber sheets or ribbons for the practice of these embodiments of the invention include a variety of prior arts for producing sheet-shaped nanofiber arrays (see references in the background description section of the invention). There are various methods. These methods include, for example, solution filtration or magnetically assisted filtration methods, deposition from volatile liquids (such as by spincoating), aggregation of nanofibers dispersed in the solution, liquids-. Sedimentation of nanofibers at the gas interface (as by the Langmüller-Blogett deposition method), deposition of nanofibers from liquid crystal assemblies in liquids, deposition of nanofibers dispersed in liquids by centrifugation, in liquids. Shear deposition of dispersed nanofibers, deposition on nanofiber aerogel sheets (including such aerogels formed directly or indirectly by CVD), and deposition from nanofiber dispersions in acids or superacids. Physical methods such as ,.

Nanofibers or nanoribbons can be formed on pre-stretched substrates by any of the chemical methods known to produce nanofibers or nanoribbons, including, for example, CVD or plasma-assisted CVD.

The nanotubes grown on or laminated with the elastic substrate can be nanofiber forests. In such cases, the nanofiber forest grows on or is laminated with the elastic substrate while the elastic substrate is either stretched or unstretched. Such application of the nanotube forest on top of the elastic substrate allows for controllable deformation of the elastic substrate, resulting in a spinnable forest.

According to Example 90, an elastically deformable nanotube sheet can be produced by the process of Example 32, and then the nanotube sheet is elastically without causing the resistance value of the nanotube sheet to be significantly dependent on the elongation of the nanotube sheet. It is shown that it can be overcoated with a second elastic silicone rubber while retaining its ability to be deformed. The importance of this illustration is that it allows the production of highly strained actuator deposits containing one or more layers of actuator material (such as electrostrained materials such as silicone rubber) and two or more electrodes. is there.

This process can be conveniently extended to elastically produce deformable deposits containing one or more nanotube electrodes laminated between elastic sheets, where the electrodes and elasticity of the alternating laminated nanotube sheets. The number of electrodes on the sheet is arbitrarily large.

The methods of this example and Example 90 can be used to produce inflatable balloons containing one or more layers of conductive nanotube sheets. To initiate the process of conducting conductive balloon formation, the first inner balloon layer is optionally inflated using gas or liquid or formed uninflated on the mandrel. It is then uninflated before the application of the first nanotube sheet.

(r) Development of artificial muscle applications The electrically conductive nanofibers in the embodiments of the invention are: (a) the material provided by the dimensional change of the material, (b) the operation of another material-the electrical energy and other electrical effects that cause the dimensional change of the output. Can be used as any of the materials that release (c), any combination of (a) and (b).

Due to the different qualities of these actuation sources, the qualities of the nanofiber yarns used in the actuation preferably vary. More specifically, for applications where the material providing the dimensional change is not the nanofiber yarn, highly twisted or highly coiled nanofiber yarn is preferred.

The first example is that the function of nanotubes in twisted yarns is to provide electrical heating that causes another material to act. In this case, the nanofiber twisted yarn is optionally highly twisted so that its contribution to yarn stiffness in the yarn direction is reduced and results in a reversible long dimensional change in the yarn direction. .. In this case, the helix angle of the twist (measured with respect to the direction of the yarn) is preferably 50 ° or more, more preferably 70 ° or more.

As an alternative to using highly twisted yarns to reduce the effect of yarn mechanical stiffness on displacements caused by the working material, nanofiber yarns have nanofiber orientation in the superposed yarns. It can be properly overlapped so as to have a large angle with respect to the direction of. FIG. 3A shows the achieved effect of the lap yarn that provides such a large angle orientation.

Materials suitable for large dimensional changes when heated are well known in the art. These include, for example, Verflx® polymers from Cornerstone Research Group Inc. (see E. Havens et al., Ploymer preprints 46,556 (2005)), aromatic polyester-based thermoplastic polyurethanes called Morthane available from Huntsman Polyurethanes. Thermoplastic polyurethane, (H.Koemer et al., Polymer 46,4405, (2005), H.Koerner et al., Nature Materials 3,115, (2004), HM Jeong et al., 37,2245 (2001), and H.Tobushi et al., 5 , 483 (1996)), Liquid crystal elasticity-(J. Naciri et al., Macromolecules 36, 8499 (2003), DK Shenoy et al., Sensors and Actuators A98, 184 (2002), and DLThomsen et al., Macromolecules 34,5868 (2001)), biodegradable shape memory polymers (see A. Lendlein and R. Langer, Science 296,1673 (2002)), oligo (ε-caprolactone) based shape memory polymer networks (A. Lendlein) Etc., Proceeding of National Academy of Science, 98, 842 (2001)), shape memory polymers based on crosslinked polycyclooctene (see C.Li et al., Macromolecules 35,9868 (2002)), and shape memory behavior. Examples of hydrogels (eg, poly (vinyl methyl ether) hydrogels, see R. Kishi et al., Journal of Intelligent Material Systems and Structures 4,533 (1993)).

The highly twisted electroconductive nanofibers of the embodiments of the invention simultaneously ensure that the use of highly twisted yarn does not excessively interfere with the operation of the yarn in the yarn direction, while at the same time memorizing the shape. Means for electrically heating such shape memory polymers to obtain material operation are provided. Shape memory polymers are preferably infiltrated into or overcoated with nanofiber threads, or both infiltrated and overcoated.

Shape memory polymers that come into contact with nanofiber threads may optionally include other conductive aids such as conductive nanofibers or particles (such as carbon black), or combinations of conductive particles and nanofibers. Can be done. These selectively used conductive nanofibers, nanoparticles, or combinations of conductive nanofibers and nanoparticles preferably electrically leach and electrically contact the strands of the nanofibers.

The elastically deformable nanotube sheet in section 10 (q) can also be used to provide electrical heating that triggers the action of shape memory polymers. The elastically deformable nanotube sheets are selectively and preferably attached to both sides of the shape memory polymer sheet. Electrical heating of these two nanofiber sheets so as to give both sheets at least about the same level of power loss (per unit area) is uniform in the length (or length and width) of the shape memory sheet. It is effectively adopted to obtain a positive change. On the other hand, electrically heating the two nanofiber sheets on either side of the shape memory polymer sheet to different degrees (or electrically heating only one of these sheets) is the shape memory sheet. Can be used to give a cantilever type bend.

As an alternative to using highly twisted nanofiber threads as electrodes for such actuators that are in the direction of the thread as the direction of action, the nanofiber threads of the embodiments of the present invention are spiral around the working material. Wrapped around. In some cases, the working material is infiltrated into the spirally wound nanofiber threads. The advantage of the spiral winding, especially the highly twisted spiral winding, is to limit the mechanical effect of the nanofiber yarn on the working stroke of the working material.

The highly electrically conductive, highly twisted nanofiber yarns of the embodiments of the invention and the elastically deformable nanotube sheets of section 10 (q) are artificially actuated primarily by gel actuators or conductive organic polymers. It can function as an electrode material for muscles. The responsiveness of this gel actuator is caused, for example, by an electrochemically occurring pH change in the liquid electrolyte that partially induces expansion or contraction of the gel due to varying degrees of hydration of the gel. Polyacrylonitrile is the material of choice for gel actuators. Methods of using this polymer are described by HB Schreyer in Biomacromolecules 1,642 (2000). Conductive polymers suitable as predominantly active materials are described by RH Baughman in Synthetic Metals 78,330 (1996) and many other literature reports.

(s) Use as a heat pipe The nanofiber yarn can be braided or simpler as a high strength and tough high performance heat pipe with highly effective thermal conductivity.

These heat pipes function like ordinary heat pipes, because most of the heat transport in them evaporates the working fluid at the hot end of the heat pipe to absorb heat energy and releases heat energy. This is the result of condensation of the working fluid at the cold end of the heat pipe. Nanofiber threads serve to allow working fluid to escape between the hot and cold ends of the heat pipe.

FIG. 105 schematically illustrates a heat pipe using a hollow braided carbon nanotube yarn wick (10501), which uses an overcoat (polymer or ceramic) that acts as an outer diffusion barrier (10502). Or by incorporating a thread heat pipe into the matrix, it is sealed by measures against loss of working fluid.

The nanofiber wick material can optionally allow wetting of the working fluid of the heat pipe, or only the outer region of the nanofiber wick, thereby allowing the inner side to act as a gas transport region. It can be treated chemically or physically as it is possible. Using this method, the laminated nanofiber threads can be successfully used as a wick. The result is that one component of the nanofiber wick provides wicking, and a second component of the wick (and the outer space relative to the unwet thread component) provides a vapor passage. That is. The yarn components for transporting fluids and vapors in nanofiber heat pipes can optionally be MWNTs, yarns, and essentially different yarns such as Kevlar® or Spectra® fibers.

Various well-known working fluids such as water and methanol can be used and have effective working ranges from -5 to 230 ° C and -45 to 120 ° C, respectively. For very hot applications there are materials such as potassium or sodium as working fluids, with operating ranges from 400 to 800 ° C and 500 to 900 ° C, respectively.

These approaches can be used to produce heat pipes with diameters less than 20 μm, but larger diameter heat pipes are more preferably used for most applications. Smaller diameter yarn heat pipes are woven into the structural fabric and incorporated into the structural fabric or into the resin as separate yarn fibers to form the yarn heat pipe / polymer matrix composite. Can be manufactured.

(t) Highly anisotropic thermal and electrical conductors and nanofiber sheets and threads as sensor arrays The nanofiber threads, sheets, and ribbons of the embodiments of the invention provide high electrical conductivity, high thermal conductivity, and high thermal diffusivity, as well as high anisotropy for their transport. These properties provide important application embodiments.

For example, the carbon nanotube sheet of the embodiment of the invention provides the following unique and unique combinations of properties that are useful as conductors of heat, temperature, and current: (1) high strength and high toughness; (2). ) High level of electrical and thermal conductivity; (3) High absorption of reversibly generated electromagnetic energy; (4) Low temperature coefficient of resistance; (5) Very low 1 / f noise, where f is AC current Frequency, which makes such conductors a very good transmission circuit. (6) High resistance to creep; (7) Intensity to hold even when heated in air at 450 ° C for 1 hour; and (8) Very high radiation that lasts even when irradiated in air Resistance.

Example 11 is given a measurement result showing high electrical conductivity of the carbon nanofiber yarn. The high electrical conductivity and high anisotropy of the carbon nanofiber sheets of the embodiments of the invention are demonstrated by the results of Example 23, where similarly, 300 as a result of the reduction in cross-sectional area resulting from densification. This coefficient, which exceeds approximately, changes the electrical conductivity, but the resistance of the sheet is a coefficient greater than 300 and hardly changes as a result of the liquid-based densification of the nanofiber sheet.

Extremely high thermal diffusivity (0.1 m) of the embodiment of the present invention (see Example 21)²Due to the high thermal conductivity (K = 50W / mK) of MWNT nanofiber sheets extracted in the solid state with D) above / s, rapid and highly anisotropic temperature fluctuations with minimal energy loss. Movement is possible for the row and / or column electrodes of the addressable sensors in the matrix (see Example 54).

The low-thickness and low-density self-supporting carbon MWNT sheets of the embodiments of the invention make very interesting bolometer materials, as shown in Example 54 and FIG. The main advantages of MWNT sheet as a bolometer material are: (1) extremely low heat capacity (low inertia); (2) high absorption coefficient over a wide wavelength range, ie 0.2-20 μm; (3) thermal radiation coefficient close to 1. (As with graphite); (4) high flexibility; (5) resistance to radiation damage; and (6) compatibility for use in high magnetic fields. At the same time, the temperature coefficient of resistivity (TCR) is low, α = -7.5 × 10-⁴ K-1 is a limiting factor for temperature sensitivity in such materials. However, it has advantages for other sensor applications and resistors with low temperature dependence.

For position-sensitive bolometers, highly aligned arrays of nanofiber sheets can be produced in a variety of ways (see Example 54 for details). For example, this can be done by (a) pulling out a highly aligned nanotube sheet from the side of the carbon nanotube forest, and (b) attaching the nanotube sheet to the two sides of the substrate, where such The substrate is a solid or flexible substrate that includes an array of metallic electrodes with a centrally rectangular opening to form opposed side sheets that are arranged orthogonally and suspended. The electrodes on these sides are coated with a temperature sensitive thin film. In one embodiment, a semiconductor film having a high temperature coefficient of resistivity, eg, VO₂Alternatively, other material is deposited on the metal electrode pad to form a series resistor with an interconnected network of carbon nanotubes. The series resistance of the carbon nanotube network and semiconductor film between the row and column electrodes is measured to produce a thermal image of the radiating object. In other embodiments, the metal pad is covered with a thermoelectric material, i.e., a complementary pair of iron on one side and a constantan alloy on the other.

Utilization of the high thermal conductivity and diffusivity of the nanofiber sheet for electronic local cooling is described in Example 59.

Section 10 (k) shows how the high electrical anisotropy of the nanofiber sheet of the embodiment of the invention can be used in a variety of applications, including pixel-segmented sensors.

(u) Nanofiber yarns and fabrics for use as cold electron cathodes for electron field emission Nanofibers, especially carbon nanofibers, are well known to be useful as field electron emission sources for flat panel displays, lamps, gas discharge tubes for surge protection, and X-ray and microwave oscillators. (WAde Heer, A.Chatelain, D.Ugarte, Science 270,1179 (1995); AGRinzler et al., Science 269,1550 (1995); NSLee et al., Diamond and Related Materials 10,265 (2001); Y.Saito, S. Uemura, Carbon 38,169 (2000); see R. Rosen et al., Appl.Phys.Lett., 76,1668 (2000); and H.Sugie et al., Appl.Phys.Lett., 78,2578 (2001)). The potential applied between the electrode containing the carbon nanotubes and the anode creates a highly localized electric field as a result of the small radius and nanofiber length of the nanofiber tip. These local electric fields cause the electrons to tunnel through the tips of the nanotubes into a vacuum. The electric field directs the field-emission electrons to the anode, where the phosphorescence selected produces light for flat panel display applications, and collisions with metal targets (for higher applied voltages) cause X for X-ray tube applications. A line is generated.

Cold electron cathodes that rely on electronic field emission from either SWNT or MWNT carbon nanofibers are well known and have already been found for commercial use (Carbon Nanotubes: Synthesis, Structure, Properties, and Applications. Topics in Applied Physics, 80, Spring-Verlag, Heidelberg, 2000, pp.391-425). The emission voltage threshold for CNT cold cathodes is very low: 1-3V / μm (J.-M.Bonard et al., Appl.Phys.A69,245 (1999)), especially Si- or Mo-microchip cathodes (50-). This is the case when compared with 100V / μm) (CASpindt J. Appl. Phys. 39,3504 (1968)). In addition, the current density of such CNT cold cathodes is very high, 10 compared to SWNT cold cathodes.⁸A / cm²And relatively high relative to MWNT cold cathodes (Y. Cheng, O. Zhou, CRP hysique 4, (2003)). The potential for applications of CNT electric field emitters in displays is very bright (RH Baughman, AAZakhidov, and WA de Heer, Science 297,787-792 (2002)), and several prototype devices have already been made containing this unique material. .. That is, the CNT-based electron source is a fluorescent lamp (AK Silzars, RW Springer, PCT Patent Application No. US96 / 13091, J.-M.Bonard, etc., Appl.Phys.Lett.78,2775 (2001), N.Obraztsov. Etc., Appl.Surf.Sci.215,214 (2003)), for X-ray tubes based on CNT cathodes (GZYue et al., Appl.Phys.Lett.81 (2),355 (2002)), and for flat panel displays (NSLee) , Etc., Diamond and Related Mater.10,265 (2001), WBChoi, etc., Technol.Dig.SID. (2000)), used. Motorola recently developed a CNT-TV, and Nano Proprietary Inc. announced a 25-inch CNT cathode-based TV. Similarly, CNTs have been found to be used in high resolution electron microscopes as very bright point electron sources with low energy diffusion (de Jonge et al., Nature, 420,393 (2002)).

For applications that require low threshold voltage and high current density from large area cathode materials, the lifetime of existing cold cathodes is relatively short and uniformity is inadequate for high resolution display applications.

A serious problem that impedes the application of these carbon nanotubes (CNTs) to cold cathodes is that they can be macroscopically shaped so that they are strong enough to effectively utilize the properties of the CNTs for field emission. There is a need for a method of assembly within the framework of a typical on-board system.

In view of many of the limitations of the prior art, the present invention relates to, in some embodiments, a cold cathode of a nanofiber yarn, a method of manufacturing the yarn cathode, and an application of the yarn cathode. By additional embodiments, the production of patterned structures of yarn, such as the numeric code of α and the special symbol (shown in FIG. 71), and the yarn in the "cathode fabric" (shown in FIG. 77). Weaving is provided. Threads for cold cathode applications can be made not only from multi-walled carbon nanotubes, but also from single-walled carbon nanotubes and a wide range of other nanofiber materials, such as conductive nanofibers and nanotubes in Section 2.

Most importantly, the thread cathode can be easily assembled into various constitutive modalities, such as, for example, one substantially vertical thread tip (or arrangement of thread tips) that emits from the ends (FIGS. 66B and 73). .. In such a geometry, the thread (7301) rises approximately vertically by a strong line of electric field (7302) rallying over the tip of the free end (7302) of the nanofiber at the cross section of the thread. When a very high voltage is applied, the current emitted by such a large number of tips is very large, resulting in light being emitted by the heated thread ends as shown in FIG.

Another geometry for cold field emission from the yarn is to place the yarn horizontally on a flat surface, with the resulting emission occurring from the sides of the yarn (Figs. 66A, 70, and 72). In FIG. 72, the nanofibers (7201) on the side of the thread and closest to the anode (7204) are their free ends (7203) due to the force of the lines of electric force (7203) emanating from the anode and concentrating on the tip (7202) at the end. 7203) is started up.

Moreover, the sides of the yarn are elongated "fluff", in which individual nanofibers and larger assemblies of nanofibers (bundles of nanofibers and assemblies of bundles) extend from the sides of the yarn (such as the sides of the twisted yarn). It can be designed to have a structure.

We have found that such fluffy structures can be produced by mechanical treatment, chemical or physical based treatment, plasma treatment, heat treatment, and electric field treatment.

Electric field treatment is particularly useful for providing fluffy yarns, which can be specially designed to include a large number of nanofibers whose free ends extend from the yarn and small diameter assemblies of nanofibers. The data show the effect of such field treatment on improving electron emission characteristics (see current curves in FIGS. 69 and 76 and SEM micrographs and schematics in FIG. 74).

The desired fluffy yarn structure is generated during the operation of the cathode in a high electric field by the force generated by the strong electric field. The electric field eventually pulls the end out of the body of the yarn and eventually partially strips the yarn (schematically shown in FIGS. 74C and 74A and 74B).

Other secondary construction modalities, such as the production of single yarns and twisted yarns, with various knots along the yarns that have the ability to superimpose a large number of yarns and adjust the electron emission characteristics in the knot region. Possible (Figures 64 and 75). In at least some cases, the thread cold cathode in the knot region was demonstrated to emit less electrons (see Figure 75 and its examples).

Some of the embodiments described herein provide novel fabrication methods, object constructions, and the use of nanofiber yarns as cold cathodes with very useful properties. For example, the carbon nanotube yarns of the present invention provide the following unique and unique combinations of properties for cold field emitting cold cathodes: (1) Number of twists in yarn and lapped yarn cathodes: High current density controllable by the number of single yarns in; (2) Very low voltage thresholds in the range below 0.5 V / micron, which can self-improve over time (Figs. 69 and 76); (3) Low operation It is a voltage, less than 300 V at a distance between a 400 micron cathode and anode; (4) a self-improving cathode in terms of current and voltage performance increase with cycles; (5). High thermal stability; (6) High mechanical strength and vibration stability; (7) Cathode patterning by thread knotting (Fig. 75) and other methods is possible, from which the thread Includes the patterning of the original nanofiber forest to which is twisted and spun; and (8) has very high radiation resistance, including radiation resistance of electron beams and UVs.

In order to increase the number of nanotube fibers on the yarn surface available for field-increasing electron emission, nanofibers in the focusing zone for spinning are optionally by electric field, or magnetic field, airflow, sound waves or ultrasonic waves, and combinations thereof. Disturbed. As a result of this disturbance, some of the nanofibers are incompletely incorporated into the yarn during twisting, so that they extend from the sides of the yarn surface (FIGS. 65 and 74). The fluffed portion 7403 in FIG. 74 has an additional free end of the nanotube and protrudes from the body of the twisted yarn (7402) that wraps the wire 7401. The result is a "fluffy yarn" in which the fluff of the nanotubes extending from the yarn provides increased electron field emission (7404) by the ends of the field emission form (as shown in Figures 69 and 76).

Fluffing yarns for field emission of electrons can also be produced by applying false twists (ie, twists that are offset by equally twisting in opposite directions) that disturb the nanofibers in similarly spun yarns. In addition, the surface of the nanotube yarn can be deliberately scraped off after the spinning is completed by a mechanical or chemical process, or a combination thereof. The nanofiber yarns of the embodiments of the invention can also be beneficially employed as a thermal emission source of electrons (known as a hot cathode), which is a cold cathode emission in that resistant heating is used to increase electron emission. Different from the source.

An additional method for producing "fluffed yarn" cold cathodes for increased field emission is to feed the nanofibers from the secondary forest to the focusing point (where the twist is formed between the yarns). As a result, nanofibers from the secondary forest tend to be incorporated in lines perpendicular to the yarn surface. Such treatment increases the intensity of electron emission as more edges are available for field emission.

According to the present specification, the mechanical toughness of carbon nanotube threads, the small diameter of the threads, and the geometry of the threads that allow the useful parts of the nanotube fibers extending from the fiber surface to provide an electric field increasing effect are nanotubes in this application. It has been demonstrated to provide the benefits of stranded yarn. For example, the geometry of the thread is as an electron emitting element for X-ray endoscopy for medical diagnostic examination, the emitting phosphor is on an outer cylinder and optionally a single thread of nanofibers in the center or It can be beneficially adopted as a central electron emission element for a cylindrical high intensity light source that is substantially coaxial with the twisted yarn (as shown in FIG. 78 of a phosphorescent lamp prototype with a yarn cathode). Carbon nanotubes are selectively particularly preferred for nanofiber yarns applied in this field emission application.

(v) Optically transparent cold electron cathodes containing nanofiber sheets for applications in displays and lamps The carbon nanotube cathode is essentially a cold cathode, and it can be widely used in applications where low power consumption and energy dissipation of narrow emitted electrons are required. Carbon nanotube emitters are rated as the best electron electric field emitters currently available. In addition, carbon nanotubes are very robust and chemically inert, and can be successfully used for such devices where vacuum or inert gas conditions are essential. Remarkable current densities have been obtained in relation to applications that require low threshold voltages and high current densities from large area cathodes.

Not all of such prior art cold cathodes are optically transparent. They are manufactured with either metal microchips such as Mo (see CASpindt J.Appl.Phys.39,3504 (1968)), semiconductors or conventional carbon fibers / nanostructures, all of which are optical. Used as a thick, opaque material.

However, most applications of cold cathodes involve the production of light that needs to be able to escape from the device, such as displays or cathode emitting sources. For example, in a normal field emission flat panel display (NSLee, et al., Diamond and Related Mater.10,265 (2001), WBChoi et al., Technol.Dig.SID (2000)), the light is coated with Al to collect charge. Emit from the phosphorescent screen. Thus, some of the electrons are absorbed in the Al layer, which erodes the efficiency of the display (it is shown in Figure 81). Similarly, high voltages must generally be applied in order for electrons to penetrate the Al layer, which is also a problem. A possible solution is to use a screen glass with ITO and a low voltage fluorescent coating. A low bias voltage can be applied by this method. However, in this case, almost half of the light is emitted back to the cathode and lost (as shown in Figure 82). Therefore, the efficiency of this type of display is also not high.

The transparent carbon nanotube (CNT) sheet of the present invention allows for different display configurations. It utilizes a transparent sheet of carbon nanotubes as a cathode, glass coated with a metal with high optical reflectance (eg Al), and a phosphor material, as shown in FIG. Therefore, almost all the light emitted from the phosphor layer by the electron impact from the cold cathode of the nanotube is directed back towards the transparent cathode (eg by the Al mirror), and the efficiency is significantly improved. Meanwhile, the low voltage region is utilized for nanoscale field emission.

The transparent carbon nanotube sheet is a backlight for flat panel field emission displays (FED), such as those extensively developed by Motorola and Samsung, or new types of high efficiency, low power consumption liquid crystal displays (LCDs). Can be used for any of the light sources. In the latter case, it is particularly important that the light passing through the transparent carbon nanotube sheet is partially polarized in the direction perpendicular to the orientation of the carbon nanotubes, as schematically shown in FIG. (Described in M.Zhang, S.Fang, A.Zakhidov, SBLee, A.Aliev, K.Atkinson, RHBaughmam, Science, 309, 1215 (2005)). This may have additional technical advantages. This is because the previously developed additional polarizing material is no longer needed in front of the thin film transistor (TFT) matrix.

Recently, in the art, additional advantages such as increased brightness, increased efficiency and reduced field voltage of field emission displays with transparent cold cathodes (if such devices were created) have been provided. It was also proposed that (US Patent Nos. 5,646,479; 6,611,093; 6,777,869; 6,933,674; 6,943,493; 6,914,381; and 6,803,708). Images formed on such displays can be viewed from both sides of the field emission display panel, allowing multiple displays to be superimposed together. However, in the above reference patent, the hypothetical emission material is opaque, and light can only pass through the cathode through a specially designed optical system and a special electrode with multiple holes. In contrast, embodiments of the present invention allow the creation of nanofiber-based, highly optically transparent cold cathodes that do not have the above drawbacks.

As described above, a method of growing both single-walled and multi-walled nanotubes as a forest of fibers in which both single-walled and multi-walled nanotubes are arranged in parallel on a solid substrate, and a method of utilizing a MWNT forest as an electron cold cathode are known. However, the resulting forest assembly has various instabilities under heavy current load, one such instability is the flash evaporation of catalyst and carbon (recently discovered by the present inventor: AAZakhidov et al., J. et al. .Appl.Phys. (submitted)), followed by spark emission of light and transfer of the CNT from the cathode to the anode, which damages the cathode.

Advances have been made in creating a robust forest of oriented CNTs on a glass substrate (Motorola, Samsung). Other methods of producing cold cathodes from CNTs include the formation of composites with polymer binders in which the CNTs are not oriented and are randomized. However, remarkable release characteristics were obtained for the polymer binder SWNT. However, the problem with polymer binders is that the nanotubes are not present in sufficient quantities to field emission into the polymer and effectively contribute to properties such as thermal and electrical conductivity. In addition, since the main component of the cathode is a polymer binder, the unique electrical properties of the individual nanotubes are weakened.

In some embodiments, the present invention relates to a cold cathode of an optically transparent nanofiber sheet, a method for producing the nanotube sheet cathode, and an application of the nanotube sheet cathode. Importantly, the yarn spinning and sheet and ribbon fabrication techniques described herein are nanofibers of various nanofiber threads, ribbons, sheets and a wide range of materials for use in a variety of electron field emission applications. (For example, WS_2,WO₂ Etc.) can be applied to manufacturing.

As mentioned above, the process of producing carbon nanotubes for cold cathodes containing nanofibers generally involves the following steps: (a) Place the nanofibers in an array selected from the group consisting of: i) aligned sequences; and (ii) sequences focused towards alignments that result in the main assembly (known as forests); (b) self-supporting from forests or other manifolds (see above for non-forest spinning). Pulling out a self-supporting nanofiber sheet; and (c) depositing the nanofiber sheet on a transparent substrate. In some embodiments, the nanotube sheet comprises carbon nanotubes.

Such carbon nanotube sheets and ribbons of the present invention provide unique properties and combinations of properties suitable for field emission by large areas of transparent cathodes. For example, controllability by doping or chemical modification to give adjustable work functions; flexibility, strength, and toughness; resistance to breakage; high levels of electrical and thermal conductivity; high energy that can be reversibly generated. Absorption; High resistance to creep, retention of strength when heated above 1000 ° C in vacuum for extended periods of time, and very high resistance to radiation and UV (especially in vacuum where cold cathodes are primarily operated). In some embodiments, the nanofibers are nanoscrolls. In some embodiments, the nanofibers are chemically and / or physically modified before or after the fabrication of the nanofiber ribbon or sheet.

The densification of the CNT sheet of the present invention, which can enhance the adhesion of the cold nanofiber sheet cathode to the substrate, makes the substrate containing the CNT sheet (or other nanofiber sheet) inorganic or ethanol, methanol, or This can be done by immersing in an organic liquid such as acetone and then drying. Such densification is effective in preventing CNTs from escaping from the substrate in a strong electric field. In some embodiments, after densification, all edges of the CNT sheet provide electrical contact to the nanofiber sheet, avoid side effects, provide mechanical connections, and others, as shown in FIG. 79. Covered with carbon conductive tape (eg, as used for SEM samples) for this purpose. A transparent sheet of carbon nanotubes (7901) is placed on an uncoated or ITO coated glass substrate (7902). The edges of the sheet are covered with SEM tape (7903) to avoid side effects. Typical emission area is 50mm²Is.

These unfavorable side effects include strong electron emission from nanofibers mechanically raised on the sides, protrusions at the ends, lifting due to high electric fields, and so due to the large field increasing factors at the protruding ends. Side effects affect the uniformity of release.

In some embodiments, the nanofibers in the focusing zone (in the extraction process) are optionally electric or magnetic, airflow, in order to increase the number of nanotube fibers on the surface of the transparent cathode sheet available for field emission. Alternatively, it can be disturbed by sound or ultrasound. As a result of this disturbance, some nanofibers are incompletely incorporated into the sheet during the withdrawal process, so that they extend laterally from the sheet surface. The result is the "fluffy surface" of the sheet as outlined in Figure 80 (top and bottom). The fluffing of the nanotubes extending from the sheet in it gives an increase in electric field and therefore an increase in field emission as described in the explanatory inset of FIG. 80. In FIG. 80 (upper part), the lines of electric field (8001) go from the anode (8002) to the end (8003) or side (8004) of the tip of a single nanofiber inside the sheet. FIG. 80 (bottom portion) provides a schematic representation of field electron emissions from the tip (free end extending from the sheet) and from the sides of the nanofibers (inside the sheet). The electrons indicated by the point (8005) are emitted from the tip (8006) and side (8007) of a single nanofiber inside the carbon nanotube sheet.

The fluffy sheet for field emission of electrons is present to some extent in the original extracted nanofiber sheet, while the numerous free ends of the nanofibers or nanofiber bundles that make up the fluffy surface disturb the nanofibers in the sheet extraction. It can be further increased by applying plasma. In addition, the surface of the nanotube sheet can be deliberately scraped off after the withdrawal is complete, such scraping is performed by mechanical and / or chemical processes. Similarly, field emission from the sides of the nanofibers contributes significantly to the total current of the sheet cold cathode (as depicted in Figure 80). The threshold electric field is greater with respect to the side emission, but the total current density from the side is significantly greater than from the edge of the fluffy sheet. Embodiments of the present invention can also be beneficially employed as a hot cathode, i.e., a thermionic radiation source that differs from cold cathodes in that resistance heating is used to increase electron emission even in small electric fields.

Transparent nanofiber sheet cathodes are particularly suitable for a variety of phosphorescent display applications, as they allow the configuration of various types of displays as shown in FIGS. 81-84. According to FIG. 81, an opaque cold cathode of normal geometry with a cathode (8102) on a glass or other substrate (8101) located behind the display, i.e. behind a phosphorescent screen (8105). Is shown schematically. Since the charge collector is an Al mirror film (8012) that contacts the backside of the phosphorescent screen, here some radiated electrons penetrate through a thin coating of Al before creating light on the screen (8105). Although lost in the meantime, in this configuration all light is emitted forward (8106) (because it is reflected from Al).

On the other hand, FIG. 82 schematically shows another normally geometrically shaped nanofiber cold cathode having a cold cathode (8202) on the back side of the display, i.e. behind the phosphorescent screen (8205). The charge collector is a transparent ITO film (8204), in which some light can be emitted backwards (8207) from the phosphorescent screen and trapped inside the device and leak out of the display. Can not. Therefore, it creates various problems such as reduction of contrast and resolution, induction of photoelectrons and similar problems.

Another preferred and promising configuration is shown in FIG. 83, which schematically illustrates the design of the new transparent nanofiber cold cathode device of the present invention. In this new configuration, the transparent cathode (8303) is on the front side of the display, and electrons are emitted towards the phosphorescent screen (8305), which is behind the observer and behind the display. The light emitted by the screen 8305 and reflected by the rear anode plate (8306) is transferred (8302) towards the observer after all have passed through the transparent cathode (8303). Since all the nanotubes at the cathode are arranged, the light passing through the arranged nanotubes is polarized perpendicular to the orientation direction of the nanotubes in the transparent cathode.

A new type of polarized backlight source is possible, as shown in Figure 84. It schematically illustrates how a transparent nanotube cathode can be used to generate polarized light relative to a normal liquid crystal display (LCD). The planar light source designed in FIG. 83 is behind the LCD display and is arranged in such a way that light passes through the transparent nanotube cathode and through the LCD. In FIG. 84, the nanotube cathode 8407 on the glass substrate 8411 evacuates the electrons towards a white phosphorescent screen (8409) placed on another glass substrate (8411) coated with the anode (8410). Is released through. The transparent cold cathode acts as a polarized fluter by the highly oriented nanotubes, so that the generated light is polarized (which is desirable for LCD operation). This light passes through the LCD components: array layer (8404), thin film transistor (8405), liquid crystal layer (8412), color filter (8402) and second polarizer (8401). Such a design eliminates the polarizer at the LCD site. This is because the polarizer is built into the backlight source.

Due to the electrical and structural robustness of the transparent nanotube ribbons and sheets illustrated herein, flexible and elastic substrates such as plastics, rubber, very thin glass, metal foils, and the like. It can be deposited on top of it in a manner that creates a flexible cold cathode that can be further processed into the desired device shape by changing the shape to match the required geometric shape. Nevertheless, the flexibility of the cold-cathode sheet allows the useful portion of the nanotube fiber extending from the sheet surface in it to provide an increasing effect of the electric field, thereby being flexible, elastic and other shapes. The advantages of nanotube sheets for this application as cold cathodes that can be adjusted to are provided.

For example, the cold-cathode geometry of the flexible sheet can be beneficially employed as an electron-emitting element for flexible X-ray endoscopes for medical diagnostic examinations, or the emitted fluorophore is optionally outside and optionally its. A flexible screen with a high intensity light source such that a vacuum space exists between these two flexible surfaces, which lies on another flexible surface that is isomorphic to the cathode of the flexible nanofiber sheet. It can be beneficially adopted as a flexible and transparent electron emitting element for use. Carbon nanotubes are particularly suitable as nanofibers for nanofiber sheets on flexible substrates for this field emission application.

(w) Flexible organic and polymer light emitting devices (OLEDs and PLEDs) that use optically transparent nanofiber sheets as charge injectors. For example, P3HT (poly (3-hexylthiophene))-based plastics with organic photocell (OPV) -like organic light-emitting devices (OLEDs) and fullerene derivatives PCBM ([6,6] -phenyl-C61 butyric acid methyl ester). Organic optoelectronic devices such as solar cells collect transparent holes or holes to replace the currently used ITO (indium-tin-oxide) and other transparent conductive oxides (TCOs). Requires injection electrodes. Such TCOs are widely used in a variety of applications where they are required with high optical transparency and electrical conductivity. However, these TCOs are brittle and, when bent, are easily damaged, even in the form of very thin coatings.

The future of using CNTs as charge injectors for OLEDs has been discussed earlier, but there are no reports on the use of nanotubes as transparent hole injectors. However, Rinzler and co-workers recently reported on the use of transparent single-walled nanotubes as electrodes for inorganic, p-type GaP light-emitting devices (AG Linzler, S. Pearton, Semiconductor Device and Method Using Nanotube Contacts, PCT International Publication No. 1). WO2005083751). Nanofibers and nanotubes were not used as transparent electrodes, but were used as components in the OLED to form a composite layer elsewhere for the purpose of increasing the conductivity of the layer. Prior art electron injectors are not transparent as they are made of microchips of either metal (eg Mo), semiconductor (eg Si), or non-optically transparent carbon nanostructures. Most of the applications involved in charge injection are for the generation of light, so such light can undoubtedly escape from the device, which is a display or lamp.

An important issue that impedes the use of transparent charge injectors or collectors for these CNTs is the method of assembling these nanotubes into a macroscopic, mechanically robust structure, and the properties of the charge injectors or collectors for the nanotubes. There is a need for a method of assembling the article into an article having a shape that can be effectively used.

The method of producing single-walled and multi-walled nanotubes as a mat or film, the method of producing carbon nanotube sheets by a solution filtration method as well, and the method of utilizing such opaque MWNT as a charge collector in optoelectronic engineering are often used. Are known. However, the resulting nanotube films and sheets are opaque, and device efficiency based on such films is inferior (as in the photovoltaic cells described in Adv. Mat. 11,1281 (1999), such as H.Ago et al.). ).

Therefore, in some embodiments, the present invention comprises a transparent nanofiber sheet charge injector for a light emitting device, a method for producing both the nanofiber sheet charge injector and the anode and cathode, and the nanofibers in the light emitting device. Regarding the application of the charge injector of the sheet. Additional embodiments provide drawers of nanofiber sheets and ribbons with very high internal interfaces and a three-dimensional network of nanofibers, and their incorporation with components of OLED luminescent materials.

Importantly, this technique for sheet and fiber extraction can be applied to the production of a wide range of nanofiber and nanoribbon sheets and ribbons in a wide range of materials for use in a variety of LED applications. Suitable devices related to applications that require low threshold voltages and high current densities from large areas have been generated for various configurations for OLEDs and PLEDs.

In some embodiments, the nanofiber sheet comprises carbon nanotubes. Optionally, the sheet composition comprises either carbon single-walled nanotubes, carbon multi-walled nanotubes, doping variants of these nanotubes, or combinations of these nanotube materials.

FIG. 85 shows a selectively preferred polymer LED configuration using transparent carbon nanotube (CNT) electrodes prepared in the solid state extraction process of Example 21. The CNT sheet (8505) is placed on a substrate (8506) of high quality display glass (Corning 1737 used for active matrix liquid crystal displays) and using a polar solvent (either ethanol or methanol). The density was increased by the method of Example 23. The polymeric film was deposited from the solution using spin coating. The hole injection layer PEDOT: PSS multilayer (8505) was deposited from aqueous solution and baked at 120 ° C for 30 minutes after each layer was deposited. The first layer was deposited at a high spin rate (6100 rpm) with a high acceleration (21000 rpm / s). This seems to "flatten" the nanotubes. Subsequent layers were similarly deposited at 6100 rpm, but at a slower acceleration, resulting in a thicker layer. The luminescent polymer (MEH-PPV) layer (8503) was spin coated from a chloroform solution (~ 0.2 wt% in chloroform) at a rate of ~ 3000 rpm. Cathode (thin metal layer, patterned with desired pixels) &lt;2 x 10^-6It was deposited using thermal evaporation of calcium (8502) and aluminum (8501) under vacuum in the torr.

The present inventors have found in the above that light emission is suppressed in the absence of PEDOT: PSS, suggesting that excitons can be quenched on nanotubes.

FIG. 68 shows another type of organic LED that uses the transparent nanofiber sheet electrode (8606) manufactured in the process of Example 21 and employs vacuum deposition of low molecular weight organic molecules. The hole transport layer (8605) of PEDOT: PSS was redeposited from aqueous solution onto a densified nanotube layer (8606) on a glass substrate (8607) using the method of Example 23. The remaining organic layers (hole transport layer, α-NPD (8604) and luminescent / electron transport layer ALq₃(8603) was deposited using thermal evaporation under vacuum. Both materials have a speed of 1 Å / s, 2 x 10^-6It was deposited under the pressure of torr. Thickness is 700 Å with respect to α-NPD, Alq₃It was 500 Å. A two-layer cathode (10 Å lithium fluoride (8602) under 1200 Å aluminum film (8601)) was deposited on top of the organic layer using thermal evaporation.

FIG. 87 shows a novel type of OLED / PLED configuration using the transparent nanofiber electrodes of Example 21. A bottom-up configuration is adopted for this device, which is possible due to the availability of self-supporting transparent nanofiber sheets of the present invention. Since this nanofiber sheet is transparent, the light emission of OLED / PLED can pass through this sheet. Therefore, the last element of this bottom-up deposition process may be the carbon nanotube sheet electrode.

The device fabrication process includes an opaque first deposition cathode layer on the substrate (double metal cathode: 8705/8704) followed by a polymer layer deposition (MEH-PPV type radiation layer (8703) and PEDOT: PSS positive. Including the hole transport layer (8702). The final deposition layer, the cathode of the transparent carbon nanotube sheet (8701), is a pressure-induced process from another substrate on top of the device (transferring the nanofiber sheet from the original substrate to the device). , Stamping) or by laying a self-supporting nanotube sheet.

Such bottom-up structures are required for certain applications, especially those that embed drive electrons on silicon wafers (eg, active matrices and thin film transistor displays). In such cases, the cathode layer cannot be deposited on top of the existing PLED or OLED. High temperatures are required for the deposition of transparent hole injectors such as indium-tin-oxide as the final deposition layer, which can damage pre-deposited polymer or molecular devices. Therefore, a low temperature or room temperature process is desired to prevent damage or morphological changes in the organic layer. The mechanical transfer of the transparent nanotube sheets described above can meet this requirement and provide an ideal solution for such display applications.

In another embodiment of the invention using the transparent nanotube sheet of Example 21, the OLED is formed completely transparent so that light can pass through the entire device. Figure 89 shows such a transparent PLED that uses carbon nanotubes for both the anode (8904) and the cathode (8901). As a result, both electrodes and the device itself become transparent.

The device can be built on a flexible / elastic substrate (8905), thereby achieving the ultimate goal of a flexible / elastic display where several OLEDs can be layered on top of each other. The device structure includes a liquid densified nanotube sheet (8904) on a substrate (8905) and a polymer layer (8903 and 8902) deposited by subsequent spin casting. The patterned nanotube cathode (8901) is then placed on top of the structure by either stamping or other transfer methods of the embodiments of the invention. This final nanotube sheet cathode should be coated with a material with a low work function (eg, with two layers of calcium or calcium / aluminum). Metals with a low work function are required at the interface for effective electron injection.

An alternative and more effective process for placing the cathode sheet on the device involves drop casting the MEH-PPV film instead of spin casting it. The corresponding solution in which the polymer is dissolved is placed on the substrate and then turned upright to allow excess solution to drain. A free-standing nanotube sheet (8901) is immediately placed on a damp film (8902). The film is then dried in an inert atmosphere. This method creates an improved interface between the MEH-PPV and the clear nanotube sheet.

The transparent carbon nanotube sheet of the present invention provides a unique property and combination of properties for charge-injected electrodes, which are extremely tough, resistant to breakage of bent parts, high electrical and thermal conductivity, and air. There is a high work function combined with very high resistance to radiation and UV, even when irradiated inside. In addition, these nanotube sheets can be pulled out as a very wide range of self-supporting, self-supporting sheets and films, which can be laminated in various ways on top of OLED configurations, reversing existing bottom-up fabrication methods. You can change to the top-to-bottom type method.

Therefore, the nanofiber sheet of the present invention can be used in a wide variety of optoelectronic applications. In some embodiments, the extraction of the transparent electrode as a self-supporting film is WO₃Or MoO₃Or MoS₂It extends to the manufacture of nanofiber and nanoribbon sheets and ribbon electrodes for a wide range of materials, such as nanofibers. This expands the range of LED applications.

Applications of the nanofiber sheet and ribbon electrodes of the present invention include the entire family of optoelectronic devices, OLEDs, PLEDs, OFETs, field effect transistors (FETs) with transparent gates, nanofiber-based batteries, fuel cells, man-made, and Electrochemical devices such as electrochromic displays can be mentioned.

In some embodiments, the present invention provides novel fabrication methods, material configurations, and applications for nanofiber sheets and ribbons with very beneficial properties for use, for example, as light emitting devices for OLEDs and PLEDs. Will be done. For example, the carbon nanotube yarns of the embodiments of the invention provide the following unique and unique combinations of properties that are useful for OLEDs: (1) High work function preferred for hole injection in the hole transport layer of OLEDs. , (2) High internal surface and porosity that binds other functional materials of the device, (3) High mechanical strength, toughness, and resistance to bending damage, enabling applications in flexible devices and electronic fabrics , And (4) Very high radiation and UV resistance even when irradiated in air.

(x) Transparent nanofiber sheets and threads as separation layers for charge collectors and photocells and photodetectors Transparent electrically conductive electrodes are required to be mechanically strong, flexible and self-supporting. Similarly, it is beneficial for these electrode materials to have an expansive internal surface, so that they are nano with other functional materials such as organic electronic materials and nanoparticles (such as quantum dots and rods). It can be connected most effectively on the scale.

It is also beneficial that the transparent, electrically conductive electrode material has an adjustable work function. Similarly, the availability of electrode fabrication means to obtain either isotropic or highly anisotropic electrode properties is that the highly anisotropic properties are electrically conductive, thermally conductive, and optically transparent. In some cases, it is especially useful.

Some embodiments of the present invention feature electrodes containing the nanofiber sheets of the embodiments of the invention, such as, for example, the transparent carbon nanotube sheets made in the solid state of Example 21. Transparent nanofiber sheet electrodes (TNSE) can be designed for applications in optoelectronic devices such as photovoltaic cells.

In another embodiment, the present invention provides a solid-state film photovoltaic cell with a built-in TNSE electrode that contributes to the photogeneration of the charge carrier as a component of functional configuration.

In some embodiments, the present invention provides photovoltaic cells that incorporate an organic semiconductor or conjugate polymer or composite between a TNSE electrode, a second electrode and the electrodes.

In an additional embodiment, the invention provides a multi-junction or tandem photovoltaic cell, which is a transparent separation layer (charge recombination layer, or interconnect) arranged between each separate single-junction photovoltaic cell. It incorporates several TNSE electrodes that separate a single junction (also known as a layer).

The present invention provides effective charge collection and charge recombination in either 3D or 2D in organic (ie, plastic, exciton, or hybrid) solar cells and articulated (ie, multi-walled) solar cells. It also relates to the application of transparent carbon nanotubes and nanofibers in combination with nanofiber threads woven into fabrics as a layer of. The TNSE electrode may be an anode and / or a cathode as an upper electrode and as a charge recombination layer in tandem.

The charge collecting electrodes of the present invention are anodes (ie, hole or positive charge collectors) in some cases, which have many advantages over prior art TOCs: they are flexible and mechanical. It is tough, has optical and electrical anodes, and has a three-dimensional network structure, making it particularly suitable for charge collection in bulk heterojunction solar cells. Furthermore, the original CNT transparent electrode has a large work function (5.1-5.3eV), which is higher than the work function (wf) (4.7eV) of ITO, and is suitable for collecting positive charges or holes.

Applicants also propose methods of using transparent carbon nanotube sheets and ribbons as electron collectors or cathodes (by special coatings or chemical modifications). Similarly, the present specification describes a method for producing the transparent carbon nanotube sheet, ribbon, and spun twisted yarn as a component of a photoactive solar cell configuration that contributes to photogeneration of a charge carrier. Additional embodiments provide spinning of self-supporting nanofiber ribbons of arbitrary size width. Importantly, these flexible and transparent electrode technologies for solar cells can be extended from a wide range of nanofibers and nanoribbons to produce different sheets and ribbons for use in different solar cell types and applications. Is.

Applications of the nanofiber sheet and ribbon electrodes of the present invention include various solar energy extraction fabrics, solar cells for hydrogen production, and solar energy extraction batteries in combination with fuel cells (as described in the examples herein). ) And so on.

Embodiments of the invention described herein provide novel construction, processing and fabrication methods, object construction, and application of transparent nanofiber sheets and ribbons with properties and functionality useful for solar cell design. Will be done. For example, the nanofiber sheets of the embodiments of the invention, especially carbon nanotube sheets, provide the following unique and unique combinations of properties that are particularly useful for solar batteries: (1) high optical transparency, (2) low. Electrical sheet resistance, (3) three-dimensional topology of mesh-like CNT networks (which allows charge collection from large volumes, not just from planar interfaces as with normal ITO electrodes), (4) charge Wide interface of 3D network to enhance separation and collection, (5) high thermal conductivity and thermal diffusivity to provide heat dissipation in solar cells, (6) positive charge in solar cells, required for hole collection High work function, (7) high flexibility to counter the brittle properties of ITO and other inorganic TCOs, (8) very high resistance to creep, (9) cermet-type non-penetration of nanoparticle electrodes It is an interpenetrating continuous form of nanofiber network that opposes the mold morphology (it is suitable for collecting charge carriers due to its bulk heterolinked configuration) and (10) heated in air at 450 ° C for 1 hour. Intensity retention, (11) Very high radiation and UV resistance when irradiated in air.

In some embodiments, the nanofiber electrode is first coated from a free-standing sheet on a flexible substrate or other substrate (as an anode or positive collecting electrode) and then coated or impregnated with a photoactive layer, which is used for charge separation. A bulk heterojunction of an organic semiconductor with a suitable donor-acceptor interface. The cathode is then deposited on top to complete the device.

In another configuration, the opaque cathode electrode is first deposited on the substrate. The photoactive layer or layer or bulk of the heterojunction interpenetrating network is then coated from the liquid phase by immersion, spin coating, inkjet printing, screen printing, or vacuum deposition. Finally, a transparent nanofiber electrode is placed on top of the photoactive layer. It is done by a stamping method described in more detail below, from a self-supporting, self-supporting sheet state in a deposited sheet state, where the sheet is placed on its surface and then pressed. Instead, a ribbon of nanofiber sheets can be placed on the device by transfer from another surface, such as carrier tape.

TNSE may be highly transparent or translucent, depending on the number of sheets and their thickness. The light absorption characteristics of TNSE can be adjusted by the length of individual nanofibers inside self-assembled nanostructures based on the antenna effect of quarter wavelength and the characteristics of directional irradiation. In addition, the light absorption intensity at the photoactive moiety impregnated in the 3D nanotubes creates a core-shell structure in which the coating of nanoparticles with a suitable metal or semiconductor or an additionally enhanced plasmonic effect is present. It can be increased by the effect of enhancing the localized electric field of photons near the nanofibers.

In some embodiments, the TNSE may further include at least one organic functional polymer such as polyalkylthiophene (PAT) or PEDOT-PSS in combination with other materials such as the fullerene derivative PCBM. .. TNSEs, such as composites of multi-walled and single-walled nanotubes, to increase functionality, such as through increased electrical conductivity, light absorption, and enhanced photoseparation of charge carriers. It may be a composite of several nanofibers.

The process of producing transparent electrodes for solar batteries involves the following steps: (a) Nanofibers to provide a substantially parallel nanofiber array with some degree of interfiber connectivity in the nanofiber array. And (b) pulling the nanofibers out of the nanofiber array with a substantially untwisted ribbon or sheet as a ribbon or sheet so that the ribbon or sheet is at least 1 mm wide.

In some embodiments, the present invention uses transparent nanofiber sheets and ribbons as organic (also referred to as plastic, exciton, or hybrid) solar cells and photodetectors and tandems (ie, referred to as). Multi-junction) in solar cells, and similarly CuInSe₂For use in charge collection and charge recombination layers in inorganic thin film solar cells such as CdTe, GaAs, or GaP based solar cells.

The charge collection electrode of the present invention is selectively preferably an anode (ie, a hole collector). The electrodes of these nanofiber sheets have many advantages over the transparent conductive oxide electrodes of the prior art: nanofiber sheets are flexible, mechanically tough and tough; they are optically and It can have anisotropy of electrical properties (or this anisotropy can be adjusted or eliminated by stacking sheets), and they are porous, which is particularly suitable for charge collection in bulk heterojunction solar cells. It can have a network structure. In addition, CNT transparent electrodes have a large work function (5.1-5.3eV), which is greater than the full work function of ITO (4.7eV) and is suitable for positive charge or hole collection.

In some embodiments, the present invention provides a method of making the transparent carbon nanotube sheet and ribbon into a flexible fabric as a component of a large solar cell structure. This can be done, for example, by including the step of filling the pores of the nanofiber electrode sheet with a conductive polymer, or other semiconductor polymer. Importantly, embodiments of the invention for transparent nanofiber sheets and ribbon electrodes are applicable to a wide range of types of electrically conductive nanofibers and nanoribbons, such as those described in Section 2.

In many embodiments, the nanotube sheet comprises carbon nanotubes. Such carbon nanotube sheets of the present invention provide high optical transparency, high alignment, toughness, high levels of electrical and thermal conductivity, for example in a very wide range from UV to infrared (300 nm-10 μm). High microwave absorption over a frequency range, substantial intensity retention even when heated in air at 450 ° C, and very high radiation and UV resistance even when irradiated in air. Such unique properties and combinations of properties are provided. In addition, these nanotube sheets can be pulled out at varying thicknesses and widths to increase their linear density (ie, weight per yarn length).

In some embodiments, the fiber or ribbon can be chemically and / or physically modified before or after the drawing or spinning process. In some embodiments, the nanofiber yarn is used by forming a composite with other materials useful for solar cell operation, such as hole-transporting and electron-transporting molecules or polymers.

(y) Doping of CNT electrodes: regulation of electrical conductivity Fermi energy (E) in electron band structures due to SWNT doping by either donors or acceptors_FIt is well known that) can be shifted to change the electrical conduction mechanism of SWNTs. Vapor exposure of alkali metals and electrochemical doping with liquid electrolytes provide a significant increase in the electrical conductivity of the CNTs doped with them.

As used herein, Applicants with those of polymer or monomeric structures impregnated with the work function of charge-collecting CNTs by improving the conductivity of transparent electrodes and creating a double-layer structure on the surface of highly grown CNTs. Describe the balance.

Applicants have demonstrated that the extremely high surface area of CNT sheets and ribbons allows for better capacitance and charge injection. The electrochemical capacitance can exceed 100 F / g, and nanofibers, sheets, and threads with such large capacitance are optionally preferred. This large electrochemical capacitance allows the electrical conductivity of CNTs to be regulated over a very wide range. CNT sheets charged in a liquid electrolyte, even when drawn from the electrolyte, washed with deionized water and dried in vacuum, as described in detail in PCT Patent Application US2005 / 007084. In addition, it retains double-layer ions on the surface of the nanotube.

Due to the narrow and limited potential windows in aqueous electrochemical doping, Applicants use non-aqueous electrochemical for severe electrochemical doping. One good candidate is LiClO in acetonitrile₄Electrolyte solution. Another very good candidate is 1-methyl-3-butylimidazolium tetrafluoroborate, which has a very wide electrochemical stability window (-2.4V to 1.7V vs. Fc / Fc).⁺) (L. Kavan, L. Dunsch, Chem. Phys. Chem. 4, 9, 944-950 (2003)).

Applicants describe a method herein comprising forming a transparent CNT sheet. To do this, the sheet is doped by charge injection in the electrolyte, the CNT sheet is removed from the liquid electrolyte, and the doped sheet is integrated with a polymer composite for use in solar cells. In the first step, a thin transparent CNT film, selectively preferably less than 200 nm in thickness, is deposited as a free-standing sheet on any substrate. Either SWNTs, MWNTs or combinations thereof can be used for this process. In the next step, the CNT sheet is electrochemically charged from the liquid electrolyte, the conductivity of the CNT sheet is increased, and the work function is adjusted. The CNT sheet is then optionally removed from the electrolyte, dried and, depending on the level of charge injection, incorporated into a device such as a solar cell.

Applicants reduced the work function of CNT electrodes by doping, for example with alkaline cations. The simultaneous pending PCT patent application US2005 / 007084 for bilayer charge injection describes in detail the process of charge injection into SWNT materials by electrochemical methods. An increased applied potential (measured with respect to potential because of zero charge injection) is required to increase the charge density. To increase the density of injections, Applicants optionally opted for the use of electrolytes with high redox stability with respect to either oxidation or reduction (depending on the sign of the desired injected charge). To do. The type of charge injected is selectively preferably holes (positive charges). This type of charge injection generally provides the highest stability for the injected charge.

Applicants optionally choose that the electrolyte used for charge injection has a high stability of electrochemical hole injection. One such preferred electrolyte is tetra-n-butylammonium hexafluorophosphate (TBAPF) in acetonitrile.₆).

The following is a typical process of embodiments of the present applicants' invention. After electrochemical charge injection into the sheet or ribbon of the nanotube, the charged electrode is removed from the electrolyte and a solvent that is stable against the charge injected into the sheet or ribbon of the nanotube (in some cases). It may be deionized water) and carefully washed. The nanotube electrodes are dried in an inert atmosphere, and in some cases such drying can be done in a heated state (selectively preferably above 50 ° C.). It is then coated with a thin layer of conjugated polymer using a two-step immersion coating method (see PCT Patent Application No./US2005/007084). First, a very thin (20-30 nm) electron block layer (such as PEDOT-PSS) is dip coated from a highly diluted aqueous solution. Heat treatment at about 100 ° C is desirable to remove water. In the next step, a resin regular P3HT polymer with very short SWNTs (preferably semiconducting) and C₆₀A 3: 1 suspension / mixture of powder is prepared, which dip-coats the charged transparent CNT electrode. The concentration of SWNTs in the shortened polymer should be below the permeation limit. In the final stage, the heat treated "sandwich" is coated and sealed with an Al electrode. In the alternative method, the deposited CNT thin film layer can be coated with PEDOT-PSS from the liquid phase. Subsequent steps can be modified depending on the charge quality, the sign of the injected charge, and the type of polymer.

As an alternative to electrochemical charge injection, charge injection to modify the conductivity and work function of the nanotube sheet electrodes (and other useful nanofiber electrodes) is chemical using electron donors or electron acceptors. It is possible in the process. Such methods are known in the art and are widely used for graphite, carbon nanotubes, and conjugate polymers.

(z) Electrochemical doping of CNT electrodes: regulation of work function Both chemical and electrochemical doping of carbon nanotubes are very attractive methods for adjusting Fermi levels by varying the occupancy of electronic states. For example, semiconductorization of CNTs can be done by p- and n-type amphoteric doping. Optical and electronic measurements indicate that for p-type doping, the Fermi level can be lowered by depleting the filled valence band or raised by filling the empty conduction band. confirmed. When the Fermi level reaches the fanhove singularity in the valence band and conduction band, the concentration of the charge carrier increases drastically. Applicants have shown modulation of the field emission IV curve of SWNT membranes by doping, thereby exemplifying the regulation of work functions. Previously about 0.4 eV Fermi level (E) for electrochemical doping of MWNTs_F) Is illustrated. A larger negative work function shift of about -1.0 eV was also observed (see PCT Patent Application US 2005/007084).

(aa) Nitrogen and boron doped carbon nanotubes for transparent nanofiber electrodes Recently, boron and nitrogen doping in both SWNT and MWNT graphene layers has received a great deal of attention. CN_XAnd CB_XThis is because the electronic properties of the tube have been found to be very sensitive to small amounts of intra-layer dopants: nitrogen as the n-dopant in the C-plane and boron as the p-dopant. To summarize the basic results, it is well known that boron and nitrogen affect not only the properties, but also the structure of the nanotubes that are doped through synthesis. So nitrogen-containing chemical vapor deposition (CVD) synthesis creates bamboo-type tubes, and boron in CVD synthesis creates longer tubes (concentrated at the tip of the tube, where boron prohibits tube closure). Manufactured. Covered walls are also observed, thus allowing interesting topologies where the walls have smooth lidded terminations. It has already been calculated, and some have been shown experimentally, during the synthesis of MWNTs, the boron atom inhibits tube closure and thus significantly increases length, as well as being a special chirality of theirs. It favors the growth of zigzag type tubes, which are all metallic.

Combined doping, which combines intra-layer doping with electrochemical or chemical non-covalent doping, is beneficially applicable. Applicants have found that charge injection into a tube by chemical or electrochemical doping is a tube property: conductivity, electron emission properties (by modulation of work function), optical and infrared reflectivity, thermal. It is illustrated that it is an important process to change the characteristics. Most importantly, the electrochemically injected charge is stable in the absence of electrolyte.

The usefulness of combination doping is CN_XIllustrated is an example of an nanotube in-sheet doped with nitrogen to produce the nanotube. CN_XNanotubes have electron-deficient levels inside the gap, resulting in such CNs by non-covalent processes._XThe charge chemically or electrochemically injected into the preform tube has increased stability.

In-sheet doping of SWNTs or MWNTs with less than 1 mol% of nitrogen, boron, or a combination thereof, is the work function, electron emission, electrical conductivity, and thermoelectromotive force of the sheet, ribbon, and thread of the nanotubes of the embodiments of the invention. Effectively applied for modification of. The degree of in-sheet doping with nitrogen, boron, or a combination thereof is selectively preferably 0.5% or more with respect to the sheets, ribbons, and threads of the nanotubes of the embodiments of the invention. This in-level doping is preferably performed prior to the fabrication of nanotube sheets, ribbons, and threads. However, it is also useful to produce sheets, ribbons, and threads of preformed nanotubes, and then optionally add other nitrogen- or boron-doped nanotubes to these articles by a secondary synthesis or infiltration process. is there.

(bb) Three-dimensional electronic fabric of nanofibers and nanofiber yarns incorporated in nanofiber sheets or ribbons Figures 95 and 96 illustrate nanofiber sheets or ribbons in which nanofibers and other electronically functional materials are incorporated into the volumetric regions of the pores of the nanofiber sheets or ribbons to increase their ability to generate light charges. Will be done.

FIG. 95 shows the conductive polymer (CP) and C in the carbon nanotube sheet to provide a heterojunction of photoactive donor acceptors in the porous transparent CNT anode (hole collector).₆₀A solar cell based on nanoscale integration is schematically illustrated. The CP / CNT wire is inside the pores of the CNT sheet, and the nanofibers in the pores function as photoelectron collectors.

FIG. 96 more reliably shows the pore volume area and the relative dimensions of the pore elements in the nanotube sheet. The inset shows the transfer of holes from the CP chain into the transparent CNT sheet anode and the electron transfer due to exciton dissociation in the intra-hole CP / CNT system. Since the charge collection length of the polymer is about 100 nm, the holes photogenerated in the holes with a diameter of about 100 nm are collected on the MWNTs of the sheet.

Chiral single-walled carbon nanotubes or WS₂, MoSe₂, And analogs thereof, can also be used to form intra-sheet heterojunctions that enhance charge collection efficiency.

(cc) Photoelectrochemical battery with charge collector and transparent nanofiber sheet and thread electrodes as layers of recombination / separation in articulated batteries In some embodiments, the present invention relates to special types of photoelectrochemical batteries, and more precisely electrodes for dye or quantum dot sensitized solar cells. Some of such embodiments relate to conductive electrodes of a special type of electrodes for dye-sensitized and quantum dot sensitized solar cells: multi-junction solar cells, also known as tandem batteries. , Counter electrode for hole collection and transparent separation layer. As a transparent electrode for charge collectors in both dye-sensitized and quantum-dot sensitized transparent carbon nanotubes and other nanofiber sheets, ribbons, and threads, and multi-junction (coupling) Methods, processes, and configurations for use as transparent separation layers (also called charge recombination layers) in dye-sensitized solar cells (also referred to as molds) are described. The additional function of the carbon nanotube charge collector for enhanced light absorption and charge generation by the nano-antenna effect in the solar cell, and other advantages are also described herein.

In some embodiments, the present invention is a regenerative photoelectrochemical battery (PEC), and more specifically, a transparent, mechanically durable, flexible nanofiber thread, ribbon, or sheet. Regarding this type of battery that uses. A PEC is an electrochemical device that generates a charge carrier by light absorption and, as a result of such light generation, creates an electrical voltage (potential difference) between two electrodes (cathode and anode).

One of the leading types of PEC is the Dye-Sensitized Solar Battery (DSC), which was first developed in 1991 by Michael Graetzel of the Swiss EPFL (Swiss Federal Institute of Technology Lausanne) and co-workers (US Patent No. 1). See 5,350,644; 5,441,827; and 5,728,487, and Nature 353,737 (1991), and Nature 395,583 (1998)). DSCs are analogs of natural photosynthetic systems and are therefore very attractive as they are inherently environmentally friendly and their manufacturing costs are relatively low compared to silicon-based and other inorganic semiconductor p / n junction solar cells. Is.

DSC obtained a very high approved conversion efficiency of 10.4%. While this battery provides high efficiency, it has some drawbacks. Current DSCs are lightweight and cannot be manufactured flexibly. However, there are many applications in which it is convenient or essential that the battery be in a solid state, be mechanically durable, and at the same time be lightweight and flexible. A major issue in the development of lightweight and flexible DSCs is the replacement of glass substrates. Glass substrates are brittle, heavy, have very low impact resistance, and are limited in shape and form.

The counter electrode (reducing electrode) in the DSC is usually constructed of an expensive transparent conductive glass substrate (about 60% of the total cost of the DSC) coated with a Pt catalyst film. Therefore, in order to reduce the cost of DSCs and expand their applications, it is necessary to develop transparent, flexible and mechanically durable electrodes on substrates other than glass. Efficiency can be increased with articulated DSCs with multiple junction configurations. The first articulated DSC containing two compartment batteries coupled in parallel was recently demonstrated (M. Durr et al., Appl.Phys.Lett.84,33). 97 (2004) and W. Kubo et al., See J. Photochem. Photobiology A 164, 33-39 (2004)).

In some embodiments, the present invention is a layer of charge collection and charge recombination in a photoelectrochemical (also referred to as Graetzel or dye sensitized) solar cell and a tandem (ie, multi-walled) version of such a solar cell. Regarding the application of transparent carbon nanotube sheets and ribbons as. The charge collecting electrodes of some embodiments of the invention are preferably anodes, i.e. holes or positively charged collectors, which have many advantages beyond prior art: they are flexible and mechanical. It is robust, has optical and electrical anisotropes, and has a convenient three-dimensional network structure for charge collection, especially in bulk heterojunction solar cells. In addition, CNT transparent electrodes have a large work function (5.1-5.3eV), which is greater than the work function of ITO (4.7eV), which is convenient for the collection of positive charges or holes.

FIG. 100 is a schematic view showing the basic structure of the dye-sensitized solar cell of the prior art. The DSC includes: (1) a first transparent substrate with each transparent electrode 10001, (2) a second opaque conductive electrode 10002 (preferably reflective) (for brevity, electrodes 10001 and 10002 indicate the first electrode and the second electrode). (3) The first electrode 10001 has a photoelectrochemically active semiconductor oxide formed in the form of a porous nanostructure formed from sintered colloidal particles 10003. And (4) photo-electrochemically active semiconductor oxides are coated with a monolayer of dye or quantum dots 10004. In both of the electrodes, the electrodes 10003 and 10002 are arranged facing each other, the sides are sealed with rubber, resin, or the like, and the space between 10003 and 10002 contains redox pairs in the usual manner. The porous structure of the semiconductor oxide 10003 is impregnated by the electrolyte in such a manner that it is filled with electrolyte 10005 and the interface between the electrolyte 10005 and the dye or quantum dot coated oxide has a very large effective interface. .. In some embodiments of the invention, the transparent substrate of electrode 10001 is coated with a transparent nanofiber sheet or ribbon.

According to the embodiments of the invention described herein, a transparent nanofiber sheet having novel configurations, processing and fabrication methods, object configurations, and useful properties and functionality in the design of photoelectrochemical solar cells. Applications are provided. For example, the carbon nanotube sheet of the embodiment of the invention provides a unique combination of properties and properties that are particularly useful for photoelectrochemical solar batteries: (1) High optical transparency (80-90%). , (2) low electrical sheet resistance, (3) high thermal conductivity and thermal diffusivity, (4) positive charge in solar cells, high work function required for hole collection, (5) brittle ITO and High flexibility to compete with other inorganic TCOs, (6) Very high creep resistance, (7) Three-dimensional morphology (convenient for collecting charge carriers due to bulk heterojunction type configuration) (8) High surface area and High electrochemical activity in terms of efficient and fast charge transfer between the electrolyte and the nanofibers due to a matched energy mechanism, and (9) very high resistance to radiation and UV even when irradiated with the electrolyte.

A new photoelectrochemical battery as described above is shown, for example, in FIG. 101. FIG. 101 is a schematic view of an embodiment of the photoelectrochemical battery of the present invention. The photoelectrochemical battery has a transparent porous nanofiber electrode 10102, wherein the nanofiber electrode is made of an active material 10103 selected from the group consisting of titanium oxide, zinc oxide, tungsten oxide and a mixture thereof. It contains a wide bandgap semiconductor electrode impregnated in the interpores, a reduction electrode with a transparent porous nanofiber electrode 10105 on a glass or plastic substrate, and a redox electrolyte 10104. ..

As the transparent substrate 10101, for example, a glass substrate or a plastic substrate such as polyethylene naphthalate (PEN) or polyethylene terephthalate (PET) can be used. As the transparent electrode 10102 formed on the surface of the transparent substrate 10101, the electrode of the transparent and porous nanofiber sheet is made of, for example, indium-doped tin oxide or fluorine-doped titanium oxide or fluorine-doped indium oxide. It is formed in place of the usual transparent conductive oxides such as. The thickness of the transparent electrode is preferably in the range of 50-200 nm. The solar light transmittance of the transparent electrode 10102 is preferably not less than 50%.

Metal oxide nanoparticles (eg 10-20nm TiO)₂The semiconductor optical electrode 10103 containing nanoparticles) is coated on the surface of the transparent porous nanofiber electrode 10102 by a printing method or a sol-gel method to form a film having a thickness of about 10-20 μm. Rapid sintering and anatase phase formation is performed by multimode microwave heating for 5 minutes at approximately 1 kW output at a frequency selected from the range varying from 2 to 30 GHz. After sintering, the layer shows a porosity of 0.5-0.65. The specific surface area of highly porous semiconductor electrodes is 20 to 300 m.²It is in the preferred range of / g. The average pore diameter of the semiconductor film is preferably in the range of 5-250 nm. When the average pore diameter is smaller than about 10 nm or higher than about 250 nm, the amount of adsorption of the optionally used quantum dot sensitizer is lower than that required for high photoelectron conversion efficiency.

In one embodiment, the monolayer of red dye molecules is ruthenium dye-II cis-dithiocyanate-N, N'-bis (2,2'-bipyridyl-, for example, at a concentration of 20 mg dye per 100 ml of solution. 4,4'-dicarboxylic acid)-(H₂) (TBA)₂RuL₂(NCS)₂(H₂O)₄ By impregnating with an absolute ethanol solution of the sensitizer, it adheres to the surface of the metal oxidation electrode of highly porous nanofibers. The impregnation process can optionally be carried out overnight at room temperature. The electrodes are washed with ethanol and then dried. The coating solution can be applied in a number of ways, such as dipping, spin coating, spraying, inkjet printing, and screen printing. The coating steps can be repeated as needed.

In another embodiment, a similar immersion step can be applied for adsorption of quantum dot sensitizers such as PbS and PbSe.

In contrast to the design of conventional photoelectrochemical batteries, dispersion of the binder component is not required for metal oxides. The mechanically robust three-dimensional properties of the transparent nanofiber sheet electrodes of the present invention provide a support grid for porous metal oxide structures that take into account the high adhesion of metal oxides to nanofibers. To. (K.-H.Jung, JSHong, R.Vittal, K.-J.Kim, Chemistry Letters 864-865 (2002)) In one embodiment of the invention, the transparent nanofiber reduction electrode 10105 in FIG. 101 is made according to the method described herein. Platinum plating of counter electrodes is not required as such nanofibers act both as charge collecting electrodes and as catalysts to enhance the electrochemical charge transfer process. The catalytic activity of the reducing electrode 10105 can be improved by coating the surface of the electrode 10105 with a thin layer of single-walled carbon nanotubes, as shown in the SEM image of FIG. 102. Both of the electrodes are arranged in such a manner that the electrodes 10103 and 10102 face each other, as shown in FIG. 101, and the sides thereof are sealed with rubber, resin or an analog thereof.

The space between the anterior and posterior reducing electrodes of clear photoactivity is normally filled with an electrolyte containing redox pairs, and between the electrolyte and a dye or QD (quantum dot) coated oxide. The porous structure of the semiconductor electrode is impregnated with the electrolyte in such a manner that the interface has a very large effective interface. Spacer particles can be inserted between the anterior and posterior electrodes to prevent electrical short circuits.

MWNT nanofiber sheets possess another unique physical property. The MWNT sheets strongly absorb microwave irradiation, as evidenced by using them in this welding of plastic parts in a microwave oven: two 5 mm thick plexiglass plates use sandwiched heating of the MWNT sheets. Welded together to provide a tough, uniform and highly transparent interface that preserved the orientation and electrical conductivity of the nanotubes. Microwave heating was performed in a 1.2 kW microwave oven operating at 2.45 GHz. Microwave processing therefore provides an attractive and highly promising method for selective heating of composite films. This technique previously used nano-sized TiO with high crystalline and monodisperse particle sizes.₂Applied to powder preparation (C. Feldman and HO Jungk, Angew. Chem. Int. Ed. 359 (2001) and T. Yamamoto et al., Chem. Lett, 964 (2002)).

In one embodiment of the invention relating to the preparation of nanofiber electrochemical electrodes, Applicants used a microwave sintering method. There, the carbon nanotube-metal oxide composite photoelectrode can be adjusted by a new low temperature sintering method by using microwave irradiation of a highly porous and conductive metal oxide film. Metal oxide (TiO₂, WO₃And ZnO, etc.) show moderate coupling with microwaves due to low electrical conductivity and low magnetic induction loss. However, carbon nanotubes absorb microwaves very efficiently and heat up rapidly. Such highly efficient CNT microwave coupling correlates with the high conductivity and nanosize of carbon nanotubes, leading to high dielectric loss. The temperature can reach 1000 ° C within minutes after microwave irradiation.

Note that the generalized energy loss equation can be written as:

<maths num="1"><img id="000002" he="21" wi="99" file="JP6312759B2_D0001.tif" img-format="tif" img-content="drawing" /></maths> Where f and ε_{o o}Is frequency and permittivity; tanσ is dielectric and magnetic loss factor, E, V_s、

<maths num="2"><img id="000003" he="11" wi="11" file="JP6312759B2_D0001.tif" img-format="tif" img-content="drawing" /></maths>Are the electric field value, volume coefficient, and shape coefficient in the sample, respectively, and microwave absorption occurs very efficiently. Thus, microwave heating of the MWNT sheet inside the matrix of metal oxides provides a tough, uniform and transparent interface with relatively little change in nanotube orientation and sheet electrical conductivity.

Opposed (reduced) electrodes are usually constructed with about 60% of the total cost of an expensive transparent conductive glass substrate DSC coated with a Pt catalyst membrane), which is brittle, heavy, low impact resistant, and in shape and morphology. Has restrictions. Therefore, in order to simplify the manufacturing process, reduce the cost of DSCs, and expand their applications (without significantly degrading performance), transparent photoelectrodes are transparent or opaque nanofiber sheets, ribbons, or threads. Can be manufactured using.

The following examples are presented to illustrate the invention in more detail and should not be construed as limiting the scope of the invention.

<p num="0571"> Example 1 This example describes a typical method for growing nanotube forests used in the embodiments of the selected invention. Aligned MWNT sequences (Nanotube Forest) were synthesized by atmospheric pressure CVD with 5 mol% acetylene in helium at 680 ° C, total flow rate of 580 NTPcc / min, for 10 minutes in a 45 mm diameter quartz tube. The catalyst was a 5 nm thick iron film, which was deposited on a silicon wafer or glass substrate by electron beam evaporation. Based on SEM and thermogravimetric analysis, the purity of the spun yarn was very high (96-98% C, in the form of MWNT), 2-4% iron and amorphous carbon, no carbon particles were observed.</p><p num="0572"> Example 2 This example describes a specific method of introducing twisting while spinning carbon nanotubes from an nanotube forest. Prior attempts to pull threads from the nanotube forest resulted in extremely weak assemblies (K. Jiang, Q. Li, and S. Fan, Nature). See 419,801 (2002) and US Patent Application Publication No. 20040053780 (March 18, 2004)). The present inventors have found that the mechanical strength increases more than 1000 times when the plying process is performed at the same time as the drawing. The present inventors also show that yarn can be produced even if the current spinning / twisting process has a diameter of 1 μm or less. The fibers of this example are twisted by attaching nanotubes from the side of the nanotube forest of Example 1 to the tip of a probe attached coaxially with the shaft of a variable speed motor operating at a typical speed of about 2000 rpm. It was pulled out by hand while hanging on. Explained in the photograph of FIG. 1 in this example, the attachment was carried out by winding a thread drawn from the nanotube forest around a small wooden spindle attached to the center of the motor shaft. By manipulating this rotary spindle, the fibers were pulled out and twisted at the same time, and the nanotube yarns from the nanotube forest were attached. The motor was mounted on the platform (Figure 1), and the platform was manually moved along the table surface to perform the withdrawal while the motor was running at about 2000 rpm and twisting. FIG. 2 is an SEM photograph showing that nanotubes aggregate into yarn during the spinning process of the present invention. There, the nanotubes are pulled out of the nanotube forest and at the same time twisted. The direction of extraction is orthogonal to the direction of the original nanotubes and parallel to the plane of the substrate. The angle between the orientation and extraction direction of the nanotubes in the forest, which is perpendicular to the substrate, decreases from 90 ° to almost 0 °, but the spinning process is sufficiently robust. The combination of yarn diameter and nanotube plying, which is several hundred times smaller than the length of the nanotubes (~ 300 μm), resulted in yarns with the attractive properties described in the other examples.</p><p num="0573"> Example 3 This example shows that very small diameter yarns can be spun using the method of Example 2. The yarn diameter is the width of the MWNT forest array, which is drawn to produce an early wedge-shaped untwisted ribbon that converges at the width of the yarn at the apex of the wedge (Figure 2) from the approximate height thickness of the forest. Was determined by controlling. Arrangement widths ranged from 150 μm or less to about 3 mm, and single yarns with diameters of about 1 and 10 μm were prepared. The 200 μm width division of the forest array creates a twisted yarn with a diameter of about 2 μm, which is 1 cm.²The forest area can produce an estimated 50m of this yarn. The inserted twist was typically about 80,000 turns / m, as opposed to about 1000 turns / m with a normal textile yarn 80 times larger in diameter. Approximately 0.8 g / cm by twisting³MWNT yarn density was obtained, which was based on direct measurements of yarn mass, length, and yarn diameter, the latter being measured by SEM. The linear density of the single yarn is typically about 10 μg / m, compared to the values of 10 mg / m and 20-100 mg / m for cotton and wool, respectively. The individual nanofibers that pass through the cross-sectional area of 5 μm diameter nanotube yarns are approximately 100,000, compared to 40-100 fibers in typical commercial wool (wosted) and cotton cross-sectional areas.</p><p num="0574"> Example 4 This example shows that the plyed fibers of Example 2 have the mechanical robustness required for superposition, and such superposition can improve the mechanical strength of the yarn. Figures 3A, B, and C show SEM images of single, double, and quadruple yarns of MWNT yarns, respectively. The twin yarn was obtained by over-twisting the single yarn and then untwisting it until the torque was balanced around itself. The alignment of the individual MWNTs along the axis of the twin yarn confirms that the dual structure is torque balanced. This method was repeated for twin yarns (in the opposite direction) to obtain quadruple yarns. FIG. 58 is a SEM micrograph showing that about 20 MWNT single yarns were twisted together to produce yarns of approximately equal diameter in human hair.</p><p num="0575"> Example 5 This example describes the retention of twist in the single and combined braided yarns of carbon nanotube yarns (using the twisted and twisted yarns adjusted in Examples 2 and 4). Unlike ordinary woven single yarns, highly twisted MWNT single yarns retain most of the twist when the yarn ends are opened (Fig. 4, top). This enhanced twist immobilization appears to reflect stronger interactions between nanotubes than between microfibers in fabrics such as cotton and wool. Particularly surprisingly, the twist is maintained up to the break point position of the single yarn and the twin yarn that are damaged by the extension of the tension (Fig. 4).</p><p num="0576"> Example 6 In this example, the pulling and twisting method of the examples of the present invention (using twisted and plyed yarns as adjusted in Examples 2 and 4) is that of nanotube yarns spun from a prior art nanotube forest. It is shown to bring about a 1000-fold increase in mechanical strength compared to the results. Untwisted yarns are weak enough to break when they are pulled away from accidentally contacted surfaces, whereas single yarns have tensile strength measurements between 150 and 300 MPa. The results of stacking (superposition) in the orientation of the nanofibers with respect to the yarn axis seemed to reflect the increase, and higher strengths between 250 and 460 MPa were observed for the MWNT twin yarns. Typical stress-strain curves for these single and twin yarns are shown in Figure 5, where curve (a) corresponds to carbon MWNT single yarn, (b) twin yarn, and (c) PVA infiltrated single yarn. To do. The stress on the y-axis in this figure is the engineering stress based on the cross-sectional area of the unstressed yarn measured by SEM. As a result of the enormous Poisson's ratio effect (described in Example 14 below), the true stress near the rupture (normalized with the true cross-sectional area near the rupture) increases by about 30%. Density normalization strength is important for aerospace applications. Maximum observed density 0.8 g / cm³When using, the density normalized fracture stress of the twin yarn is 310-575MPa / gcm³Between.</p><p num="0577"> Example 7 This example shows that the single-walled and twisted yarns of the nanotubes of Examples 2, 3 and 4 have toughness comparable to the high-performance polymer yarns used in bulletproof vests. Pure nanotube threads have much higher breaking stresses (up to 13%) than graphite fibers (~ 1%). Combined with this fracture stress and high fracture strength, the work required to break the yarn (called toughness) is equally high: 14 J / g for single yarn, 20 J / g for twin yarn, It was 11 J / g for PVA infiltrated single yarn, which combined high strength with low fracture strain (about 3-4%). The toughness of twin yarns (20J / g) is higher than that of graphite fibers (12J / g), making it a commercial fiber used in bulletproof vests (~ 33J / g relative to Kevlar® fibers). Close but much greater toughness was illustrated for solution-spun SWNT / PVA composite fibers (600 J / g). However, the latter energy absorption is mostly due to irreversible plastic deformation involving large strains, and such large deformations are necessary but such energy absorptions can occur only once.</p><p num="0578"> Example 8 This example shows that carbon nanotube yarns can be easily braided (see Figure 3E) and can be knotted hard (Figure 6). Abrasion and knotting, especially one knot, includes most polymer fibers and yarns (including the yarns used in Kevlar® and Spectra® fibers and bulletproof vests, customary textile yarns, and Even a single polymer chain breaks at the entrance of the knot) significantly reduces the strength, but the single and twin yarns of the nanotubes studied are not so, pull breaks are inserted and far from a single knot. It was only observed from a distance. High wear resistance is suggested by the absence of extreme tensile breakage in long thread loops pulled by a very stiff single knot.</p><p num="0579"> Example 9 This example does not utilize the methods and nanotube properties described in the embodiments of the present invention for twisted nanotube sheet strips (cut parallel to the orientation direction) as compared to Examples 2, 37 and 52. If the desired increase in mechanical properties is not given. Aligned films with cut sheet strips are magnetically oriented assemblies of micron-length nanotubes (see JEFischer et al., J. Appliied. Phys. 93, 2157 (2003)). Similarly, we continue from the sides or tops of these magnetically oriented nanotube sheets or sheet strips using a pull-out direction in which the longer nanotubes of the embodiment of the invention can be pulled out and twisted. The nanotube thread was not pulled out.</p><p num="0580"> Example 10 This example shows that the mechanical properties of the twisted yarn can be enhanced by infiltration of the polymer, polyvinyl alcohol. The yarn used was made in Example 2. MWNT / PVA composite yarns were made by immersing the yarns in 5 wt% PA aqueous solution for 15 hours, or by passing the yarns through droplets of this solution during spinning and drying. The molecular weight of PVA was in the range of 77000-79000, with 99.0-99.8% hydrolysis. The observed intensity of single yarn increased to 850 MPa due to PVA infiltration. A typical stress-strain curve for the PVA-infiltrated nanotube yarn of this example is shown in Figure 5c. In FIG. 57, an SEM micrograph is given showing that PVA infiltration does not split the structure of the twist base of the MWNT yarn.</p><p num="0581"> Example 11 This example shows that the nanotube-based twisted yarn has high electrical conductivity both before and after conversion to nanotube / poly (vinyl alcohol) composite yarn (using the method of Example 10). The threads studied (2 μm to 10 μm in diameter) had 4-probe electrical conductivity of about 300 S / cm and negative resistance temperature dependence (about -0.1% between 77 and 300 ° K) at room temperature. PVA infiltration reduced the electrical conductivity of the yarn by only about 30%, resulting in nanotube / PVA composite fibers with electrical conductivity more than 150 times higher than observed for nanotube composite yarns containing insulating polymers. I arrived.</p><p num="0582"> Example 12 In this example, (a) the twisted yarn of carbon nanotubes has a dramatically increased elastic strain region as compared with the high-strength carbon nanotube yarn of the prior art, and (b) this long elastic region makes the toughness of the yarn. On the other hand, it is shown that a high elastic recovery component is provided, and (c) the reversible deformation of the yarn is hysteresis. When subjected to a loading and unloading cycle, the nanotube yarn shows a hysteresis stress-strain curve (Fig. 7). Complete unloading of the initial load does not return the yarn to its original length, but the initial hysteresis loop does not substantially shift in subsequent cycles. Depending on the initial strain, the observed energy loss per stress-strain cycle of MWNT twins ranges from 9-22% for 0.5% cycle strain and 24-28% for 1.5% cycle strain. (Figure 8), and in the 39-48% range for the highest reversible cycle strain (2-3% for total strain up to 8%). Within the hysteresis loop, the effective modulus at initial no-load and initial reload is much higher than for the final part of no-load and reload (Fig. 9). Similarly, in relation to the application, the breaking strength of nanotube yarns (single and double yarns) was unaffected up to 50 loading and unloading cycles in the stress range of 50% of the breaking stress. Unlike nanotube sheets made by filtering nanotube solutions, nanotube threads are resistant to creep and associated stress relaxation. When the nanotube twin yarns are held at 6% strain (170 MPa initial stress) for 20 hours, the stress is relaxed by more than 15%, and this small stress relaxation occurs within the first 20 minutes and is mostly viscoelastic (ie, reversible). )Met.</p><p num="0583"> Example 13 This example illustrates the extreme stability of mechanical properties of a stranded nanotube yarn at high temperatures, as well as the retention of properties at critical temperatures. These yarns were produced by the method of Example 2. The breaking strength (300 MPa) of the twin yarns did not change substantially after heating at 450 ° C for 1 hour. Although evidence of oxidation was clear on SEM micrographs, the nanotube threads held at 450 ° C for 10 hours were strong enough and flexible enough to be knotted. A tight knot knot was also possible while the nanotube yarn was immersed in liquid nitrogen.</p><p num="0584"> Example 14 This example illustrates that the inventor achieved a huge Poisson's ratio to the carbon nanotube yarn spun in Example 2. They observed a huge Poisson's ratio for nanotube yarns, which increased from 2.0 to 2.7 for single-walled MWNT yarns and 3.3 to 4.2 for twin yarns with increasing stress (Figure 10). These Poisson's ratios measured while stretching the yarn in SEM are up to 12 times higher than those observed in the orthogonal direction with respect to normal individuals. The Poisson's ratio of 4.2 means that the elongation of the thread at strain ε gives 4.2 times the strain in each lateral direction, and the fraction volume decrease 7.4 ε for about 0.4 ε of the normal solid fraction volume increase. Means that Thus nanotube threads are stretch-densified, which is extremely rare for solids. A bulk search survey of 500 crystal phases revealed that only 13 were elongated-densified (RH Baugham, S. Stafstroem, C. Cui, SODantas, Science). See 279,1522 (1998)). Elongation-Densification materials must have a negative linear compression ratio, in which case the yarn length increases when the yarn is hydrostatically compressed in a non-permeable hydrostatic medium. Means to do. These huge Poisson's ratios and the accompanying elongation-induced volume reduction to 7.4ε are due to the regulation of absorbency and permeability of nanotube yarns and fabrics by applying small strains in the yarn direction (or more than one). Will be available for. We have described the application of this stretch densification to the manufacture of electronic devices (usually these novel knots to obtain the patterning capabilities obtained for electronic devices using photolithography). (Using knottronics).</p><p num="0585"> Example 15 This example illustrates the application of nanotube spun yarn by plying / drawing process (Example 2) and superposition (Example 4) for filaments of incandescent lamps. FIG. 18 is a diagram of twin threads of multi- walled nanotubes electrically heated to incandescence in an inert atmosphere chamber . The thread is wound between two metal reeds separated by about 20 mm and silver paste is applied to the thread at the junction with the metal reeds to reduce resistance. The filament thus formed emits light when a voltage is applied. This has been known since the days of Thomas Edison, but it is the first example of using a high toughness twisted yarn for this application (see Example 7 for the measurement result of the toughness of the twisted yarn). The existence of this toughness makes it possible to manufacture incandescent light bulbs that are more resistant to filament breakage due to mechanical damage than ordinary incandescent light bulbs.</p><p num="0586"> Example 16 This example draws carbon nanotubes from a multi-walled carbon nanotube forest to form a nanotube ribbon and wraps this nanotube ribbon around a mandrel (hollow capillary tube) to produce the transparent article of FIG. Illustrate that. Using the nanotube forest of Example 1, we have found the surprising finding that nanotube ribbons of any width can be pulled out of the forest, and that these ribbons are optically transparent. The width of the resulting ribbon was essentially equal to the width of the sidewalls of the nanotube forest pulled from the forest untwisted. These ribbons are sufficiently mechanically robust and easy to handle without damage. Figure 11 shows an approximately mm wide nanotube ribbon spirally wound over a 1 mm diameter glass capillary tube. The transparency of the ribbon is indicated by the visibility of the lines printed on the paper sheet beneath the glass capillary tube around which the nanotube ribbon is wrapped.</p><p num="0587"> Example 17 The method of Example 16 can be used to make hollow tubes that can be used for neuron-like cell proliferation. Although prior art has well demonstrated the suitability of nanotubes for cell proliferation, this feature is important because there has been no description of how to make a properly shaped nanotube assembly for this purpose. The hollow tube containing the nanotube ribbon can be adjusted as in Example 16. The selection of the mandrel is made to facilitate subsequent removal of the ribbon wrapped around the columnar mandrel. Sufficient layers of nanotube ribbon to provide the required mechanical strength can be wound with either a helix or two opposing helices. The mechanical strength of the spirally wound ribbon can optionally be enhanced using the liquid densification process of Example 23. The wrapped nanotube ribbon can then be removed from the mandrel to provide a hollow tube suitable as a substrate for cell proliferation. This removal from the mandrel can be performed in a variety of ways. One method is to use a mandrel, which is a polymer that depolymerizes and evaporates at low temperatures. Another method is to coat the glass capillary tube with a coating that easily solubilizes it, and its decomposition allows the hollow tube with the nanotube ribbon to slip from the mandrel.</p><p num="0588"> Example 18 This example illustrates the fabrication of MWNT ribbons deposited over a very wide width on a glass substrate to provide a transparent, electrical conductive film. This very wide ribbon is drawn from the nanotube forest of Example 1 by pulling a forest sidewall section approximately equal to the ribbon width. Details regarding the various methods by which the inventor was able to perform this withdrawal are given in Examples 21 and 46. FIG. 17 depicts a nanotube sheet after being mechanically pushed into a glass substrate. The electrical and optical properties are anisotropic because the nanotubes are well aligned in the sheet. The print is on a white paper sheet underneath the electrical conductive film. The visibility of the print shows the transparency of this electrically conductive sheet.</p><p num="0589"> Example 19 This embodiment describes a method of making a twisted yarn that is an electrochemical device such as a supercapacitor or a battery. A single yarn of carbon nanotubes (Example 2) is over-twisted in an amount sufficient to form a twin yarn (as in Example 4). While retained at the tension used in the plying process, the plying is exposed to an aqueous solution containing polyvinyl alcohol and phosphoric acid or other known medium suitable as an electrolyte. This exposure results in absorption of the electrolyte precursor into the yarn and overcoating on it. The remaining liquid is then optionally removed by evaporation to form a solid or gel electrolyte. The opposite end of the electrolyte-coated fiber is then brought out together to allow twisting-relaxation to form the twin yarn. In it, the electrolyte coating prevents direct lateral electrical contact between the two single yarn components that make up the twin yarn. If the electrolyte is mechanically too resistant to this twist and is automatically generated, the two yarn fragments are wound together in the other twisting process. The twin yarns are then optionally overcoated with additional electrolytes. The loop ends of the twin threads are then cut so that the two fibers are electrically separated from each other and only contacted via the electrolyte gel. The two electrically separated, electrolyte-filled single yarns in the twin yarns may be able to act as counter electrodes for fiber supercapacitors. As an alternative to the above process, the two single yarns are coated and absorbed with an electrolyte, optionally partially dried, and then side-by-side before the selective step of twisting each other or overcoating the fiber pairs with an electrolyte. There is a method of contacting and combining. Implementation of the latter method for untwisted nanotube fibers is AB Dalton et al., Nature 423, 703 (2003). A method similar to the manufacture of fiber batteries can be used. However, in order to achieve high energy storage densities of such fiber supercapacitors, the electrolytes used in the above process are optimally selected to have a high redox stability range and are the salts of the electrolytes. As the component, it is preferable to select a lithium salt of the type usually selected for lithium batteries.</p><p num="0590"> Example 20 This example shows that, in some cases, the surface tension effect of the absorbed liquid can be used to densify the nanotube yarn before plying. After pulling the nanotubes out of the forest, they are passed through a liquid bath or exposed to liquid vapor. Liquids suitable for such densification of yarns pulled from the forest of Example 1 include methanol, isopropyl alcohol, and acetone. Evaporation of the liquid absorbed by the yarn causes lateral shrinkage, leading to higher densities. In Example 38, the inventors obtain a uniformly twisted yarn by densifying the drawn ribbon before twisting, even when the applied twist is very low (corresponding to a 5 ° spiral angle). Show that you can. In the absence of a preliminary application of liquid yarn densification, the application of such low twists results in non-uniform twists and yarn diameters.</p><p num="0591"> Example 21 This example shows that a continuous, transparent nanotube sheet with high strength can be drawn from the side wall of the multi-walled nanotube (MWNT) forest of Example 1. The MWNTs were 10 nm in diameter and the forest heights studied ranged from 50 to 300 μm. The withdrawal was initiated by contacting the MWNTs torn from the forest sidewalls using an adhesive strip. Sheets up to 5 cm wide, meter long, were then hand-pulled at 1 m / min (Fig. 21). The transparency of the sheet is illustrated by the visibility of the Nanotech Laboratory logo behind the MWNT sheet. Only ~ 2.7 μg / cm²Despite these area density measurements, these 500 cm²The seat is self-supporting between the drawers. A 1-centimeter-long forest with a height of 245 μm was converted into a self-supporting MWNT sheet with a length of about 3 meters. Using a linearly moving stage that was automated to perform withdrawals up to 10 m / min by winding the sheet over a centimeter-diameter rotating plastic cylinder, the sheet production rate was increased to 5 m / min. The sheet making process is very robust and it is clear that there are no basic restrictions on seat width and length: if the withdrawal speed was less than 5 m / min, the resulting 5 cm seat width would be forest. It was equal to the width. The nanotubes are highly aligned in the withdrawal direction, as shown by the streaks in the SEM micrograph of FIG. This withdrawal process does not work for most types of MWNT forests and the maximum permissible withdrawal speed depends on the structure of the forest. Intermittent bundle formation in the forest is beneficial, in which individual nanotubes move from one bundle with several nanotubes to another. The bundled nanotubes are simultaneously withdrawn from different altitudes in the side walls of the forest together with the nanotube bundles that reach the top and bottom of the forest, minimizing the resulting fractures in the fibril (Figure 22 and). twenty three). The disordered regions in the top and bottom of the forest, where some nanotubes loop, help maintain continuity. For forests with similar topologies for different forests and nanotube lengths in the 50-300 μ range, longer nanotubes (corresponding to higher forests) were easiest to pull out to the sheet. Probably because the increase in the length of the nanotubes increases the mechanical bonds between the fibrils in the sheet.</p><p num="0592"> Example 22 This example shows that the nanotube sheet of Example 21 extracted in the solid state contains an airgel containing novel and previously unknown useful object states: highly oriented carbon nanotubes. Approximately 2.7 μg / cm²The volumetric measurement density is about 0.0015 g / cm from the measured area density and sheet thickness of about 18 μm.³Is. Therefore, the as-produced sheet is a transparent, durable, electrically conductive, highly anisotropic airgel. The high degree of orientation of nanotubes in the nanotube sheet is illustrated by the Raman spectrum of FIG. There, four as-produced sheets are stacked, with all sheets having the same orientation. A VV arrangement (polarized light parallel to the incident ray and Raman signal) was used with parallel polarized light (||) or vertical polarized light () with respect to the extraction direction of the nanotubes. The ratio of the G-band Raman intensity (632.8 nm excitation) to polarization parallel or perpendicular to the extraction direction is 5.5 and 7.0 for the VV configuration (polarization parallel to the incident ray and Raman signal). Between. And this corresponds to 0.69 and 0.75 for each of the four superpositions studied (Fig. 41). Similarly, the anisotropy of light absorption (Fig. 25) showed high anisotropy for the nanotube sheet. Ignoring the light scattering effect, the ratio of absorption coefficients for parallel and perpendicular polarization to a single sheet as it was drawn increased monotonically from 4.1 at 633 nm to 6.1 at 2.2 μm. The streaks parallel to the extraction direction in the SEM micrograph of FIG. 22 provide more evidence for advanced nanotube orientation with respect to the as-extracted nanotube sheet.</p><p num="0593"> Example 23 It is shown that it can be easily densified into a highly oriented transparent electrically conductive sheet having 5 g / cm3. We have placed a as-produced sheet in contact with a flat substrate (eg glass, many plastics, silicon, gold, copper, aluminum, and steel) and simply adhered to it, with the MWNT sheet attached. Is immersed in a liquid (eg, ethanol), the substrate is withdrawn from the liquid and then evaporated to obtain a 360-fold increase in density. Densification of the selected area of the entire sheet or within the sheet also causes such liquid to be dropped or otherwise injected onto the sheet area desired to be densified and evaporated. It is easy to obtain. For the MWNT sheet prepared as described in Example 1, the airgel sheet is shrunk to a maximum thickness of 50 nm due to the surface tension effect during the ethanol evaporation period. SEM micrographs taken at right angles to the sheet plane suggest a slight decrease in nanotube orientation as a result of densification. But this observation is easy to make mistakes. This is because crushing a sheet of about 20 μm into a sheet of about 50 nm without changing the lateral dimensions of the sheet causes out-of-plane deviations in nanotube orientation to be noticeable in-plane deviations in SEM micrographs. The airgel sheet can be effectively bonded to the substrate by contacting the selected region with ethanol, and the airgel sheet can be densified by evaporation. Adhesion is strengthened by crushing the airgel thickness as the contact area between the nanotubes and the substrate increases. For certain types of nanotubes, the functionality of liquids that do not effectively affect the densification of liquid-based sheets, ribbons, or threads can be enhanced by the addition of appropriate surfactants. For example, water does not work satisfactorily for densification of nanotube sheets prepared from the nanotube forests of Example 1 using the method of Example 21. However, a surfactant / water mixture (0.7% by weight Triton X-100 in water or 1. in water. Either 2% by weight lithium dodecyl sulfate) was a satisfactory densifying agent. Another consideration for selecting a liquid for densification is the viscosity of the liquid, which affects the speed of the liquid infiltration process, and the ease with which this liquid can volatilize during subsequent processes. .. Very surprisingly, the sheet resistance in the pull-out direction (Fig. 24) changes by &lt;10% due to the densification of the sheet by a coefficient of ~ 360, which increases the transparency of the sheet (Fig. 25). The anisotropy ratio of sheet resistance decreases from 50-70 for non-dense sheets to 10-20 for densified sheets, but this anisotropy ratio for densified sheets is almost temperature invariant.</p><p num="0594"> Example 24 For purposes of comparison with nanotube sheets produced by the techniques of the present invention, this example demonstrates the application of conventional filtration-based processes for the production of SWNT and MWNT sheets. In another embodiment, we will compare the properties of these normally adjusted sheets with those of the present technology. The forest growth MWNTs of Example 1 were used in the filtration-based sheet making process. The latter sheet, produced by the filtration route, was a mixture (of 0.07% by weight MWNNT) dispersed ultrasonically in an aqueous solution containing 0.7% by weight Triton® X-100 as a surfactant. Was used. SWNT seats are (HiPco, Carbon Manufactured in a similar manner using carbon monoxide synthetic nanotubes (obtained from Nanotecnologies, Inc.). Prior to measurement, the residual surfactant was removed from these MWNT and SWNT sheets by thermal annealing in argon at temperatures up to 1000 ° C. Thermogravimetric analysis of forest-induced MWNTs in oxygen shows that they contain up to 4% non-combustible weight, which appears to be due to catalytic particles. The weight% of the catalyst in HiPco nanotubes is ~ 30%.</p><p num="0595"> Example 25 This example shows that the as-pulled and densified MWNT sheets have very low resistance temperature dependence and low noise power density, which makes these MWNT sheets extremely suitable for sensor applications. Represent. In fact, the temperature dependence of sheet resistance is almost the same for forest-extracted and densified nanotube sheets and sheets manufactured by filtration routes using the same forest-grown MWNTs, manufactured by filtration. It is much smaller than the single-walled nanotube sheet (Fig. 24). In addition, the low frequency (f) noise power density in the pull-out direction of the densified forest pulled-out sheet is 10.⁴It is 10 times lower than the normal filtration production sheets for SWNT and MWNT respectively (Fig. 26).</p><p num="0596"> Example 26 This example shows that forest-drawn MWNT sheets are preferably assembled in a biaxially reinforced sheet array. These sheets were prepared using the method of Example 21. A four-ply, two-axis reinforced sheet arrangement is shown in Figure 27. The chiral structure, which appears to be optically active for long-wave infrared and microwave, stacks parallel sheets so that the orientation direction spirals along the thickness direction of the stack, followed by individual stacking arrangements. It can be manufactured by increasing the density of the sheet so that the sheet thickness is about 50 nm.</p><p num="0597"> Example 27 This example shows that the mechanical properties of airgel analogs and densified MWNT sheets are unexpectedly high, even if these sheets are without binder material. Density normalized mechanical strength is measured much more accurately than mechanical strength. This is because measuring the sheet thickness is less reliable than the ratio of the maximum force to the mass per length in the elongation direction. Non-densified sheet deposits are 120 and 144 MPa / (g / cm)³) Has the measured tensile strength. The strips for measuring the mechanical properties of the MWNT sheets as they were pulled out were cut from one original sheet and stacked so that they had a common nanotube orientation direction as shown in Part A and Part B of FIG. Part A shows engineering stress-strain, showing surprisingly small changes in maximum stress on samples containing different numbers of sheet strips stacked on top of each other. The true fracture stress of these samples is obtained by multiplying the engineering fracture stress by the ratio of the length at break to the initial length, which is 120 and 144 MPa / (g / cm).³) Changed. Part B in Figure 29 shows the highest force and corresponding strain in Part A as a function of the number of stacked sheet strips for the experiment. Density deposits containing 18 co-oriented sheets are 465 MPa / (g / cm)³), And the strength when adjacent sheets in the sediment are orthogonally oriented to produce a densified biaxial structure is 175 MPa / (g / cm).³) Decreased. These density-normalized strengths are used for ultra-lightweight aircraft and have been proposed for solar sailing vessels for space applications (see DE Edwards et al., High Performance Polymers 16, 277 (2004)) Mylar® and Kapton®. Film strength ~ 160MPa / (g / cm³), And ultra-high strength steel sheet (~ 125MPa / (g / cm)³)) And aluminum alloy (~ 250MPa / (g / cm)³)) Already comparable or larger.</p><p num="0598"> Example 28 This example also illustrates the high mechanical properties of the carbon nanotube sheet. FIG. 30 is a photograph showing that the as-pulled nanotube sheet supports millimeter-sized droplets of water, orange juice, and grapefruit, where the masses of the millimeter-sized droplets are in contact. It reaches 50,000 times the mass of the nanotube sheet. The airgel region beneath the aqueous droplets was densified during the evaporation of water.</p><p num="0599"> Example 29 This example shows a stable, polarized, UV, visible, and infrared incandescent lamp (FIGS. 31A and B) for sensors, infrared beacons, infrared imaging, and reference signals for device calibration. The polarization of the emitted radiation to the as-extracted sheet with 2.5% elongation increased from 0.71 at 500 nm to 0.74 at 780 nm, which was previously for 600 μm long MWNT bundles with an ejection length of ~ 80 μm. Substantially higher than the degree of polarization reported in (0.33 at 500-900 nm). The wavelength dependence of the light intensity for both polarizations matches the predicted functional form of blackbody radiation, and the degree of polarization is significantly independent of the sheet temperature between the observed temperature ranges of 1000K and 1600K. The cost and efficiency benefits of reducing or removing the need for a polarizer, and the MWNT sheet provide a spatially uniform emission over a wide spectral range that is otherwise difficult to achieve. The low heat capacity of these very low mass incandescent emitters allows them to be switched within an observation of less than 0.1 ms in vacuum, providing a current-modulated optical output with a shorter time schedule.</p><p num="0600"> Example 30 This example shows polymer welding by heating a transparent MWNT sheet sandwiched between plastic parts. MWNT sheets absorb microwave radiation strongly, as evidenced by their use in welding plastic parts in microwave ovens. MWNT sheets are sandwiched between two 5 mm thick Plexiglas® plates and welded together using heating to maintain the orientation and electrical conductivity of the nanotubes, tough, uniform and highly transparent. Interface is provided. Microwave heating was in a 1.2KW microwave oven operating at 2.45GHz. The input power was controlled by using water as a reference, linearly raising the temperature of the water to 100 ° C in 3 minutes, holding this water temperature for 1 minute, taking the sample out of the furnace and lowering it to the ambient temperature. .. Figure 33 shows that the sheets sandwiching the MWNTs were welded together using microwave heating, resulting in a tough, uniform, transparent interface with little change in nanotube orientation and sheet electrical conductivity. A 5 mm thick plexiglass (potimethyl methacrylate) plate is shown. The combination of high transparency and superthermal stability provides advantages not found over the conductive polymers used in previous microwave-based welds. This microwave heating process can be used to produce polymer composites, electrically heated car windows, and antennas in car windows with high transparency from polymer sheet deposits separated by nanotube sheets. The nanotube sheet can be conveniently attached to the surface of the plastic or other meltable material, and in the plastic the nanotube sheet is sandwiched between the low melting point polymers and only the low melting point polymers are nanofibers. It is selected to melt as a result of the temperature increase caused by the absorption of radiation from the sheet or electrical contact heating. In these processes, plastics are selected so that they do not provide significant microwave absorption in the microwave frequency range used.</p><p num="0601">Example 31 This example demonstrates that the as-pulled MWNT sheet can be easily brought into contact with conventional adhesive tape to produce an optically transparent adhesive appliqué used for electrical heating and to provide microwave absorption. Shown. Furthermore, this example shows that these conductive polymer appliqués can be bent strongly without significantly changing the electrical conductivity. The conductive appliqué can be produced by placing an undensified MWNT sheet (adjusted as in Example 21) on an adhesive-lined tape and pressing it. Instead, an undensified MWNT sheet was simultaneously pressed and attached to the adhesive backing tape and substrate. The ratio of the peel strength after MWNT lamination to the peel strength without the intermediate MWNT sheet is 0.7 mm thick with respect to the aluminum foil duct tape (Nashua® 322) on the polyethylene terephthalate sheet used as the overhead transparent material. For transparent package tape (3M, catalog 351L) adhered to the Al sheet, 0. It was 9. Due to the porosity of the MWNT sheet, the peel strength is largely retained when the undensified MWNT sheet is laminated between the adhesive tape and the surface of the contact plastic or metal. FIG. 34 is a photograph of a transparent non-density MWNT sheet used as an electrically conductive and microwave absorbing appliqué. The MWNT sheet is pressurized against the adhesive tape (transparent Scotch packaging tape from 3M), which extrudes the adhesive on the tape through the pores in the MWNT sheet, giving adhesive performance to another surface (this). If 110 μm thick polyethylene terephthalate sheet). The UTD is printed on a paper sheet under the appliqué to illustrate transparency. This appliqué is important for electrical resistance in the movie taken about the MWNT appliqué (a non-density MWNT sheet sandwiched between a transparent packaging tape (3M, catalog 351L) and a 110 μm thick polyethylene terephthalate sheet). It is shown that it can be repeatedly folded on itself without causing a large increase. This ability to bend without degradation of electrical conductivity is important for flexible electronic circuits and is not found in ordinary transparent conductors such as indium tin oxide. The metal strip in FIG. 34 is an electrode used for contact formation with the nanotube sheet. Highly folded configuration from unfolded configuration (top photo) (bottom photo, paper clips in the photo are used to maintain the highly folded configuration).</p><p num="0602"> Example 32 In this embodiment, a transparent carbon nanotube sheet is converted into a highly elastically deformable electrode, as an electrode for a high-strain artificial muscle and to convert a high-strain mechanical deformation into electrical energy, and a large amplitude. Illustrates the method used for the adjustable damping of mechanical vibrations. The exemplified actuator material is silicone rubber. 1mm thick silicone rubber sheet (Smooth-On's ECOFLEX (Manufactured using 0040) is stretched to 105% strain, and then one as-pulled MWNT sheet (adjusted as in Example 21) provides self-generated adhesive contact prior to strain relief. Overlayed to do. Nanotube sheets can optionally be densified by a claimed liquid-based densification process without the unfavorable effects of targeted elastic properties. As shown in FIG. 35, the initial sheet resistance value of the silicone rubber / MWNT sheet composite material obtained without load was 755 Ω / . However, after an initial increase of resistance ~ 6%, the resistance changed below 3% during the subsequent 4 strain cycles up to 100% strain. Ordinary conductors are hardly able to undergo such large strains without losing electrical contact with the working material. Conductive grease is used to maintain electrical contact with electrostrained actuator materials that generate 100% or more strain (R. Pelrine, R. Kornbluh, Q. Pei, and J. Joseph, Science. 287,836 (2000)), on the other hand, these greases are not suitable for use as electrodes on electrostrained sheet deposits that can generate large forces and high strains without the need for thousands of volts of applied voltage. Further experiments show the general applicability of this method of providing highly elastic electrodes on an elastically stretchable substrate. For example, the installation of 120% stretched elastic spandex® fabrics (prepared as in Example 21) of non-walled nanotube sheets (by pressing and then subsequently in the liquid-based high density of Example 23). (By application of the chemical process) results in an nanotube electrode material that can be elastically relaxed and repeatedly re-elongated to the initial elongation without undergoing substantial resistance changes. One or more carbon nanotube sheet layers can be applied on top of the spandex layer without adversely affecting the performance of the nanotube sheet layer. Suitable spandex® fibers and / or fabrics are DuPont (and called Lycra®), Dorlastan Fibers LLC, INVESTA, and Radici. Made by Spandex Corporation.</p><p num="0603"> Example 33 This embodiment illustrates the use of MWNT sheets manufactured in a solid state as hole injection electrodes for polymer light emitting diodes (PLEDs), which are a special type of organic light emitting diodes (OLEDs). Free-standing transparent MWNT sheets are manufactured using a solid state process and placed on a clear glass or polymer substrate to produce flexible or rigid PLEDs. Two active polymers were used in the device: PEDOT / PSS and MEH-PPV. PEDOT / PSS is poly (3,4-ethylenedioxythiophene (PEDOT), which is doped with (poly (styrene sulfonate) (PSS). PEDOT / PSS is a 1-3% solids-containing aqueous dispersion. Obtained from HC Stark as, and sold under the trade name Bayton® P. MEH-PPV is synthesized by known methods (CJNeef, JP Ferraris, Macromolecules). 33,2311 (2000)), which is poly (2-methoxy-5- (2'ethyl-hexyloxy) -p-phenylene vinylene). PEDOT / PSS is used for flattening during sheet densification of MWNT sheets as they are drawn out, and as a hole transporter and buffer layer, which reduces the barrier to hole injection from MWNTs. .. MEH-PP acts as a photoelectron radiation zone. PEDOT / PSS was first spin cast onto MWNT seats. (250 rpm for 1 minute, then 760 rpm for an additional 1 minute to remove excess solution). After drying at 110 ° C for 1 hour, a radiation layer of MEH-PPV was deposited in a second spin casting process (30 seconds at 3000 rpm). After drying the MWNT sheet assembly overnight in an inert atmosphere, a device cathode was added, which consisted of two layers of calcium (30 nm) and aluminum (20 nm), each of which was continuously deposited by thermal evaporation. Luminance characterization of the above device shows a low turn-on voltage of 2.4 volts and 500 cd / m²The highest brightness of was shown. Similar devices were constructed using PEDOT / PSS and MEH-PPV, but without the MWNT sheet they were very resistant and showed no light emission. Devices made without the PEDOT / PSS layer, which penetrate the MWNT sheet and provide hole transport and flattening, exhibit high brightness, but require higher turn-on voltage and shorter device life. FIG. 36 shows a polymer-based OLED that uses a MWNT sheet made in a solid state as a hole injection electrode. The transparent MWNT sheet, PEDOT / PSS, and MEH-PPV assemblies cover the entire image area, while the Ca / Al cathode is only on the emission dots. Typical brightness is 350 cd / m²(At 15mA), which is an additional 500cd / m²Was increased to. Increased hole injection is caused by high local electric fields on the tips and sides of the nanotubes and three-dimensional interpenetration of the nanotube sheet and device polymer. Hole injection was limited to one plane for inorganic light emitting diodes prior to the use of nanotube sheets (K.LEE, Z.Wu, Z.Chen, F.Ren, SJPearton, AG, Rinzler, Nano Letters See 4,911 (2004)).</p><p num="0604"> Example 34 In this embodiment, the as-pulled MWNT sheet is transferred onto non-porous paper, and the as-pulled sheet is densified to produce an electrically conductive printing tape containing the MWNT sheet. It is shown that it can be used for a printing electronic circuit on a flexible substrate. A self-supporting MWNT sheet (made by the method of Example 21) is placed on a non-porous paper ((WWR2005 Catalog No. 12578-121), used in the laboratory for weighing samples). And densified using the liquid infiltration / liquid evaporation route of Example 23 of the present inventor. After densification, the airgel nanotube sheet shrank to a thickness of ~ 50 nm, forming a mechanically durable electrically conductive layer. The densified sheet was turned inside out and placed on standard writing paper and a sharp object was used to write on non-porous support paper. The nanotube sheet was transferred from non-porous paper to plain paper (Fig. 37). Most importantly, light microscopy of the transferred nanotube sheet area shows that the arrangement of nanotubes on the printing tape is retained in the nanotube pattern transferred to the porous paper. Thus, the orientation of the nanotubes in the transferred circuit pattern can be freely controlled by changing the relative orientation between the image generation and image transfer sheets. In this embodiment, the image generation sheet is a non-porous paper overcoated with a nanotube sheet, and the image transfer sheet is a porous paper to which the nanotube sheet portion is transferred. Undensified nanotube sheets can also be used for printed electronic circuit elements (simply excluding the densification process). This process is less attractive than that using densified sheets. This is because the nanotubes were transferred to the part of the porous paper that was not under the writing tool. Nevertheless, the transcribed nanotubes are bound more tightly to the porous paper than the accidentally transcribed ones, where the latter is easily swept away without disturbing the deliberately transcribed nanotubes.</p><p num="0605"> Example 35 In this example, the nanotube sheet produced in the process of Example 21 has a network in which a bundle of nanofibers branches and recombines with other branches to have lateral connectivity orthogonal to the withdrawal direction. Indicates that it is a kind of self-organizing woven fabric to be formed. The SEM micrograph of FIG. 28 shows this branching and branch recombination. The deviation of the fibril from the pull-out orientation is scale-dependent and therefore appears more at this high magnification than at the lower magnification. The fibril branch is continuous through the sheet, thereby creating an essentially interconnected fibril network that extends laterally.</p><p num="0606"> Example 36 This embodiment illustrates that a MWNT sheet ribbon produced by drawing out in a self-supporting solid state can be conveniently pulled out and twisted to form a large diameter yarn having a uniform diameter. A 10.5 cm long, 3 cm wide, as-pulled nanotube sheet (made as in Example 21) is folded over itself along the sheet pull-out direction to approximately the same length. Manufactured a pseudo-circular assembly with. One end was attached to the tip of the spindle and the other end was attached to a fixed copper wire. By introducing twisting, uniform spun yarn was formed at a twisting level of ~ 2000 turns / meter. The diameter of the obtained spun yarn was about 50 μm. The resistance change from untwisted to 5000 turns / meter twist is about 12%, showing that the interconnected fibril network provides most of the electrical pathways in the yarn (Figure 47), formed by the twisting process. The new contact has been shown to be a less important determinant of electrical conductivity.</p><p num="0607"> Example 37 This embodiment describes a method of drawing out carbon nanotube yarn and spinning a twisted yarn from a high-density nanotube sheet attached to a substrate. The advantage of such a process is that it allows the fabrication and storage of nanotube sheets. Three layers of as-extracted self-supporting MWNT sheets (manufactured as in Example 21) are placed on a substrate (eg glass, plastic, or metal foil) and using a liquid (in Example 23). (Process use) Higher density. Plastic substrates such as Mylar were most suitable. The desired width of the densified sheet was easily stripped from the substrate using adhesive tape to initiate the pull-plying and spinning process. By twisting one end of the stripped sheet strip and attaching it to a motor that pulls out the yarn at the same time, a spun yarn having a uniform diameter was obtained. This process can also be extended to produce thicker yarns by simply increasing the number of as-pulled nanotube sheets that are initially laminated together. The number of stacked sheets was increased from 3 to 5 then to 8 sheets.</p><p num="0608"> Example 38 This example shows that the tensile strength depends on the spiral angle obtained by the twisted yarn, and the main advantages of increasing the density of the yarn by the liquid treatment. When used as the yarn was untwisted and pulled out of the forest, the mechanical strength of the yarn was too weak to be measured by our equipment. Similarly, the densification of the ribbons drawn before twisting makes it possible to obtain yarns of uniform thickness and uniform twist from these ribbons, even when the applied twist is very low. Became. Applications of such low twists (corresponding to a spiral angle of 5 °) in the absence of pre-applied liquid-based yarn densification resulted in non-uniform twists and diameters. The experimental results obtained are shown in FIG. The data points in FIG. 48 depicted using circles correspond to diameters in the 18-20 μm range where the circles were spun using the method of Example 2. The yarns were densified using liquid treatment to obtain sufficient mechanical strength to measure untwisted data (shown in squares). Untwisted yarn was obtained from a ~ 5 mm wide ribbon drawn from the forest of Example 1 and then densified with ethanol (as was done on the nanotube sheet in Example 23). In this embodiment, this rather wide range of ribbons was used, but the described strengthening effect also applies to narrower yarns. The effect of this liquid treatment (including filament densification during liquid absorption and liquid evaporation) dramatically increased the strength as well as the tensile strength. The resulting yarn showed a non-circular cross section. Since the 5 ° twisted yarn could not reach a uniform twist along the length, this sample was also densified with ethanol after the twisting. As can be seen in FIG. 48, the peak tensile strength ~ 340 MPa can be achieved at a spiral angle near 20 °. Without pretreatment of the liquid (as described in the nanotube sheet of Example 23), the data points for zero twist in Figure 48 would be near zero on the tensile stress scale. Similarly, the 5 ° twist data points in the absence of solvent densification would correspond to a significantly reduced strength. Excessive twisting also reduces strength, as shown in FIG. Adding a 70 ° twist to the untwisted yarn reduces the tensile strength in half. The high twist reduced the breaking stress, but had a higher strain than the moderately twisted yarn as shown in FIG. 49 (measured tensile strain with the same sample in FIG. 48). Very importantly, the data in Figure 48 (square data points) show that liquid treatment provides useful strength even when twisting is not applied.</p><p num="0609"> Example 39 This example shows that the tensile strength of the yarn decreases with increasing diameter of the yarn. The method of spinning the yarn is similar to that of Example 2. The diameter of the yarn is controlled by the width of the ribbon being spun, and the data points in Figure 50 correspond to the ribbon width in the 3-27 mm range. Since the tensile strength of the yarn depends on the twist angle, the twist angle was kept constant while the yarn diameter was changed. As can be seen in Figure 50, high twisted (~ 50 °) twisted yarns (triangular data points) have a lower strength with increasing yarn diameter than lower twisted yarns (~ 15 °) (round data points). More difficult to receive. Break strain is weaker and the dependence on yarn diameter is negligible. The yarn consistently breaks independently of the yarn diameter near 10% strain (Fig. 51).</p><p num="0610"> Example 40 This example shows that the twist dramatically increases the tensile strength of the yarn, even if the twist is subsequently removed by receiving and removing equal twists in the opposite direction. Both threads shown in Figure 52 were tuned from the same nanotube forest and ribbon of the same width (using the method of Example 2). Therefore, the number of fibrils passing through the cross section of the thread was retained. The twist on yarn A is 26000 turns / m clockwise, with a twist angle of 28 °. A 26000 turn / m clockwise twist on yarn B was first introduced by forming a lock stabilizing yarn, and then the same twist was introduced counterclockwise to release all twists. It should be noted here that the increase in yarn diameter as a result of twist deinsertion (comparing the SEM micrographs of A and B in FIG. 52) is relatively small. The pulling force of the breakage on thread A is 24 mN and that on thread B is 14 mN. The resulting tensile strength is 339 MPa for thread A and 113 MPa for thread B. The tensile strength of the untwisted yarn is too low to be measured by our equipment, and these measurements show that the net effect of twisting and untwisting dramatically increases the tensile strength and maintains the twist. Indicates that the tensile strength can be further increased. Since strong untwisted yarns are strongly desired for use in the formation of nanotube / polymer composites with both high strength and high toughness, false twisting (insertion of twists that continue to deinsert and remove twists later) is the yarn strength. This amazing finding that can dramatically increase is very important. This discovery motivates the development of the false twist spinning apparatus described in Figures 44-46.</p><p num="0611"> Example 41 This example shows that a carbon nanotube (CNT) sheet can be pulled out from a forest attached to a substrate film (plastic, metal foil, Teflon (registered trademark) film, etc.) to increase the density and wind the mandrel. Illustrative examples of the feasibility of this process are given in Examples 23, 31, and 32 for no adhesive, adhesive coat, and elastic substrate, respectively. Figures 53 and 54 give a schematic description of such a process. Element 5302 in Figure 53 is a calibrated nanotube forest as described in Example 1. Element 5301 is a growth substrate, element 5303 is an nanotube sheet drawn from the forest, element 5304 is a substrate film, and element 5305 is an nanotube sheet attached to the substrate film. The attached nanotube sheet is densified using a liquid (element 5306), dried on a heater (element 5307) and then wound onto a mandrel. Here the rollers (2) are represented by white circles and the mandrel (3) are represented by filled circles. By repeating the process, the multi-walled nanotube sheet can be applied to the substrate film. A variant of that process is illustrated in Figure 54. Instead of liquid, liquid vapor (element 5406) is used to densify the collected sheet and the densified sheet (element 5407) is wound onto the mandrel. The elements are the substrate for the nanotube forest (5401), the nanotube forest (5402), the CNT sheet (5403), the substrate film (5404), the CNT sheet attached to the substrate film (5405), and for the supply of steam. Heating system (5406), densified CNT sheet on substrate film (5407), mandrel for feeding substrate film (5408), roller for integrating nanotube sheet and substrate film (5409), and collecting mandrel (5410). ). Each roller in FIGS. 53 and 54 is optionally a pair of rollers, one on each side of the laminated nanotube sheet and substrate film. Can be replaced. Importantly, the densified nanotube sheets manufactured by the equipment in Figures 53 and 54 are later rewound from the mandrel for yarn twist-based spinning to form self-supporting densified sheets. (See Example 37), or separation from the substrate film for mechanical transfer of selected portions of the nanotube sheet to other substrates (see Example 34). Similarly, the substrate may be an elastic film (or woven fabric) stretched prior to attachment of the nanotube sheet (see Example 32), or an adhesive coated substrate sheet (see Example 32). Stretching can be performed by controlling the relative rotation speed of the substrate feed and the winding mandrel of the substrate film / nanotube sheet and the rollers (or pair of rollers) between these mandrel.</p><p num="0612">Example 42 In this example, the nanotube sheet is pulled out of the forest, attached to an adhesive coated substrate film, sealed with a second film (such as plastic, metal foil, or Teflon® film), and wrapped around a mandrel. The process taken is illustrated. FIG. 55 is a schematic diagram of the process. Element 5502 in FIG. 55 is an nanotube forest tuned as described in Example 1. Element 5501 is a growth substrate, element 5503 is an nanotube sheet drawn from the forest, element 5504 is an adhesive-coated film 1, and element 5305 is an nanotube sheet attached to an adhesive film 1. The attached nanotube sheet is sealed with film 2 (element 5506), and the sandwiched nanotube sheet (element 5507) is wound around the mandrel. Film 2 is later separated from the nanotube sheet / film assembly. Due to the porosity of the nanotube sheet, the tape adhesiveness remains, and the nanotube sheet with the adhesive sheet can be suitably applied to a desired surface. In FIG. 55, the rollers are represented by white circles and the mandrel is represented by solid circles.</p><p num="0613"> Example 43 This example illustrates a method of spinning a single yarn of carbon nanotubes from the sides of two nanotube forests. The two nanotube forests were placed in close proximity so that the tops of the forests were either in contact with each other or closest to each other between the nanotube forests. Narrow nanotube ribbons were simultaneously pulled out of these two stacked forests and attached to the tips of the spindles, twisted and pulled out simultaneously to give a single yarn of unwound nanotubes.</p><p num="0614"> Example 44 This example shows a method at the start of drawing out the nanotube sheet. First, a straight line is scratched onto the back surface of a silicon wafer substrate, which is optionally used for nanotube growth, and the wafer is broken down into two forest sections. The two forest sections are then separated, preferably orthogonal to the original scratch direction. Since the nanotube bundles are interconnected in the forest, the nanotube sheet is formed between the two sidewalls of the forest. In this configuration, the allowable sheet production rate can be doubled because the nanotubes are supplied from both sides. Scratch lines can be manufactured before or after forest growth.</p><p num="0615"> Example 45 This embodiment illustrates a method in which deposits of carbon nanotube sheets can be deposited on the contour surface, the surface can be densified, and the contour shape is maintained in the shape in the nanotube sheet array. For example, the application of this example allows the deposition of carbon nanotube sheets as a layer in contour composites (such as aircraft panels), as contour heating elements for aircraft ice protection, or for energy storage and automotive contour panels. It can be used as a contour supercapacitor that provides both structural components. The contour surface used in this illustration was an egg-shaped plastic bottle. The major and minor axes of the oval cross section were 4.1 cm and 2.7 cm at the bottom, and 3.6 cm and 1.8 cm at a height of 4.3 cm from there. The lower part division of the bottle was used for the contouring process. Absorbent material (one of two layers of cellulose tissue paper) was wrapped around the bottle. After wetting the tissue with isopropyl alcohol, an undensified 4 cm wide nanotube sheet (adjusted as in Example 21) was wrapped around the side surface of the bottom of the bottle. (The orientation direction of the fiber is the circumferential direction). The isopropyl alcohol was dried, which densified the nanotube sheet in a bottle shape. This process was repeated 20 to 30 times to produce densified deposits of nanotube sheets with the shape of the bottom region of the bottle. The nanotube sheet deposits maintained their bottle shape even when the nanotube sheet and attached tissue paper sheet were removed from the bottle mandrel. When the load was further applied to flatten the sheet deposit and then the load was removed, the contour shape was restored.</p><p num="0616"> Example 46 This example describes a method for initiating the extraction of a sheet, ribbon, ribbon array, thread, or thread array of nanotubes from an nanotube forest using an adhesive, pin array, or combination of adhesive and pin array. Will be done. Interestingly, we find that contacting the adhesive tape with either the top or side wall (edge) of the nanotube forest helps to provide mechanical contact that allows the initiation of sheet withdrawal. Find out. Using the nanotube forest prepared as in Example 1, various adhesive types worked well for sheet drawers, with adhesive to 3M's Post-it Note, Scotch Clear Tape (3M's). 600), Scotch packaging tape (3M3850 series), and Al foil duct tape (Nashua 322). Linear contact of the adhesive strips (so that the adhesive strips are orthogonal to the pull-out direction) is particularly efficient for initiating the pull-out of a sheet with a high degree of structural perfection. The reason why this top contact method is particularly beneficial is that the nanotube forest typically has non-linear side walls, and the adhesive strips are linear (or linear with properly spaced pins). This is because its use (in an array) provides linear contact with the forest drawer. A tightly spaced pin arrangement is also effectively employed to initiate the withdrawal of the seat. In one experiment, the pinout consisted of a single line of pins. In this case, the mechanical contact required for spinning was initiated by the partial insertion of a straight pin array into the nanotube forest. The pin diameter was 100 microns, the pin tip was less than 1 micron, and the spacing between adjacent pin tips was less than 1 mm. Satisfactory seat drawers were achieved using pin insertions between 1/3 and 3/4 of the forest height (in the range between 200 and 300 microns). Using linearly arranged adhesive patches or linearly arranged pins separated into each compartment, Multiple ribbons or threads can be started in the same way. The separation distance between the adhesive patches along the length of the linear arrangement is the width of the ribbon or yarn production (eg, twist-based spinning, false twist-based spinning, liquid densification-based spinning, or these. Determine the width of the sheet strip used for the combination). Mechanical separation of sheet strip patches or pin patches in a linear arrangement is effectively employed at the start of the drawer to avoid interference during processing of adjacent ribbons or threads, such as during the introduction of twists. Adhesives with different lengths along the peeling direction to produce yarns of different diameters (possibly combining different yarns of different diameters to produce lap yarns) by pulling out and twisting adjacent strips. The use of agent patches (or pin patches) is effectively adopted. Different degrees of twist and direction of twist are selectively preferably applied to different single yarns drawn using a compartmentalized adhesive or pin strip. These different single yarns can optionally be superposed on yarns containing a freely selected number of superpositions. Importantly, the use of the above method of laminating single yarns of different diameters can be used to produce highly dense lapped yarns. This is because smaller diameter single yarns can help fill the voids between larger diameter single yarns. The use of adhesive patches (or pin patches) with different lengths along the peeling direction is effectively employed to produce (manufacture). Different degrees of twist and direction of twist are selectively preferably applied to different single yarns drawn using a compartmentalized adhesive or pin strip. These different single yarns can optionally be superposed on yarns containing a freely selected number of superpositions. Importantly, the use of the above method of laminating single yarns of different diameters can be used to produce highly dense lapped yarns. This is because smaller diameter single yarns can help fill the voids between larger diameter single yarns. The use of adhesive patches (or pin patches) with different lengths along the peeling direction is effectively employed to produce (manufacture). Different degrees of twist and direction of twist are selectively preferably applied to different single yarns drawn using a compartmentalized adhesive or pin strip. These different single yarns can optionally be superposed on yarns containing a freely selected number of superpositions. Importantly, the use of the above method of laminating single yarns of different diameters can be used to produce highly dense lapped yarns. This is because smaller diameter single yarns can help fill the voids between larger diameter single yarns.</p><p num="0617"> Example 47 This example shows that the spun nanotube yarn of the embodiment of the invention can be easily inserted into a normal woven fabric, thereby providing an electrical interconnect, a sensor, and other electrical elements to the woven fabric. The light micrograph of FIG. 42 shows two MWNT yarns (including a single yarn with a diameter of 12 μm) inserted into a normal woven fabric containing a melt-spun filament with a diameter of 40 μm. The insertion method is performed by tying a nanotube yarn (manufactured in the process of Example 4) to the end of the filament in the original fabric and pulling the filament out of the fabric so that the nanotube yarn is drawn into the fabric.</p><p num="0618"> Example 48 This embodiment exemplifies a novel continuous spinning apparatus in which twisting is introduced while fine and ultrafine nanofiber yarns are wound on a bobbin. The device is outlined in Figure 38, "Elaboration on Twist Insertion and Filament Storage Methods during. Described in Section 5 of "Spinning". The spinning device in this embodiment is a spindle, a donut-shaped take-up disc attached to a take-up yarn guide, an electromagnet, and a donut-shaped metal magnetic disk that comes into contact with a spindle base, which is typically made of steel and is a ferroelectric substance. Equipped with. The donut-shaped take-up disc has a diameter of 20 mm and a thickness of 3 m. Robins used are typically 5 mm in diameter and 30 mm in length. The spindle is driven by a variable speed DC motor, controlled via a computer interface and has a top speed of 15,000 rpm. Electromagnets are used to introduce variable braking force into the take-up disc, reducing the angular velocity relative to the spindle. The rotation of the drawn nanofiber assembly around the spindle shaft introduces the twist to form the yarn, and the slower rotation of the take-up disc winds the yarn onto the spindle. The advantage is that the twist level and spinning speed can be controlled independently by the electronic interface that regulates the motor speed and the applied magnetic field. With this system, the tension applied to the spun yarn can be minimized, and the spun yarn can be handled with a high or low braking force. The same device can be used to superimpose a large number of single-strand yarns to continuously produce multi-single-strand yarns. In that case, the nanotube forest is replaced with a reel of unplyed yarn.</p><p num="0619"> Example 49 The inventors find that too low a density of nanotubes in the forest makes it difficult to spin as yarn or withdraw as ribbon or sheet. This is illustrated in Figure 56, where SEM micrographs of the growth substrate are compared for spinnable forests and virtually non-spinnable forests (after removing the nanotubes). Here, the small-diameter holes on the growth substrate correspond to the growth points of MWNTs. The nanotube diameter (about 10 nm) is about the same for both these spinnable forests and virtually non-spinnable forests. However, we found that the areal density at the base of the nanotube forest was 90-200 billion nanotubes / cm for a highly spinable nanotube forest.²In comparison, 9-12 billion nanotubes / cm for low density nanotube forests that are difficult or impossible to spin.²Was observed (counting the pit density on the growth substrate). Similarly, we have a higher proportion of forest base area occupied by nanotubes (7% -15%) for highly spinnable forests, which makes spinning difficult or impossible. It was observed to be 1.1% -2.5% of the total nanotube forest.</p><p num="0620"> Example 50 This example demonstrates that nanotube sheets can be deposited on a substrate, densified using a liquid infiltration method, and peeled off the substrate to give a free-standing densified sheet array. The importance of this example is that it allows the storage of densified nanotubes on the mandrel and the removal of this densified sheet from the sheet substrate (typically a plastic film carrier) for subsequent use. That is. The as-extracted 3, 5, or 8 layers of free-standing MWNT sheet (manufactured in Example 21) are placed on a substrate (eg glass, plastic or metal foil) and densified using a liquid. (Using the process of Example 23). Plastic substrates such as Mylar film are most preferably used. Any desired width (or full width) of the densified sheet is easily stripped from the substrate using adhesive tape to initiate the sheet removal process.</p><p num="0621"> Example 51 In this example, a very thin densified carbon nanotube sheet deposit (less than 150 nm in thickness) is wrapped around a mandrel for storage, shipped, and then a carrier sheet without a supporting substrate during this operation for use. Attached (such as the Mylar film of Example 50) Indicates that the nanotube sheet can be rewound. In this illustration, two free-standing densified nanotube sheet deposits are pressed (after being stripped from the Mylar film substrate in the process of Example 50), and the two nanotube sheet deposits tend to stick to each other. It was provided by observing that it was not.</p><p num="0622"> Example 52 This example shows that liquid densified nanotube sheet deposits can be formed with cellulose tissue paper, the nanotube sheets or ribbons are easily stripped from the cellulose substrate, and these ribbons can be twisted to make durable nanotube yarns. The sheet deposit / tissue laminate studied was produced as in Example 45. Despite the resulting contours of the nanotube sheet stacks formed on the mandrel of oval cross section, the full width (4 cm) or narrow ribbon of the nanotube sheet deposits could be pulled out uniformly from the cellulose tissue substrate. Ribbons drawn from the tissue substrate were twisted (3 mm and 5 mm wide) to produce durable nanotube threads.</p><p num="0623"> Example 53 This example illustrates a twist-based method of producing a fiber composite of two different fiber materials. One is electrically conductive carbon nanotubes and the other is electrically insulating cellulose microfibers. Similarly, the present embodiment illustrates a method of imparting either insulating microfibers or electrically conductive carbon nanofibers to the outer surface of the twisted yarn. Further, this illustration shows how the carbon nanotube yarn is coated on the insulating layer. Similarly, replacing the cellulose sheet with a similar sheet containing meltable polymer microfibers (polypropylene or polyethylene-based non-woven paper), the method of this example is on nanofibers in yarn by heat or microwave heating. Can be used in the production of polymer / nanotube composite yarns that are twisted or false twisted prior to polymer melting. A deposit of tissue paper / nanotube composite contoured using the method of Example 45 is used for this illustration. Ribbons 3 mm wide from the composite deposit are cut parallel to the nanotube orientation and twisted to give a medium strength yarn. Due to the contouring on the oval mandrel (having the nanotube fiber orientation in the circumferential direction), the inventors (depending on the twisting direction) of the insulating cellulose microfibers or electrically conductive carbon nanotubes. We found that either one appeared on the surface of the twisted yarn.</p><p num="0624"> Example 54 This example describes the application of a highly anisotropic carbon nanotube sheet for manufacturing a bolometer. Nanotube assemblies are used as heat distribution materials rather than as sensitive materials. Extremely high thermal diffusivity (0.1 m) of the solid state drawer MWNT nanofiber sheet of the present invention (see Example 21 for adjustment)²D) above / s and thermal conductivity (K = 50W / mK) allow rapid temperature fluctuations to highly anisotropic columns and / or minimized energy loss of the row electrodes of the matrix addressable sensor. become. The electrical signal is established through heating at the nanotube sheet electrode interface. The process of forming a thermal image display is shown in Figures 59A-C. Figure 59A shows a self-supporting MWNT sheet 5902 suspended between two holders 5901 and 5902. The substrate 5904 of FIG. 59B (acting as a frame supporting two orthogonally arranged nanotube sheets) is made of an insulating dielectric material such as polycarbonate or glass fiber sheet. The row metal electrode pads 5906 are formed on top of the substrate 5904. The row electrode pads 5905 are formed on the other side of the substrate 5904. The temperature sensitive layer 5908 is formed on the electrode pad with a material that is responsive to temperature fluctuations. In some embodiments, the temperature sensitive layer is formed of vanadium dioxide (or other suitable semiconductor material). Vanadium dioxide exhibits a large temperature coefficient of resistance at room temperature and changes the series resistance of the entire circuit consisting of the metal electrode / semiconductor layer / nanotube assembly / semiconductor layer / metal electrode. In other embodiments, the temperature sensitive material 5908 is formed of a thermocouple material (eg iron) on one side of the electrode and costantan on the other side. The carbon nanotube assembly supplies heat to both sides. The thermocouple layer converts temperature fluctuations into thermoelectric potential differences. Once the electrodes are formed, the highly aligned MWNT nanofiber sheets are attached to both sides of the substrate by arranging the nanotube arrangements of the respective sheets so that they are orthogonal to each other. The highly anisotropic thermal and electrical conductivity of suspended MWNT sheets minimizes lateral crosstalk between nanofiber orientation and orthogonality, enabling high-resolution imaging of thermal radiation objects.</p><p num="0625"> Example 55 In this example, how very low 1 / f (f: frequency) noise and low temperature coefficient of resistance (see Example 25) can be made using MWNT carbon nanotubes as precision registers according to some embodiments of the present invention. Illustrate whether it can be applied. Figure 60 outlines the device. A free-standing MWNT sheet 5902 (possibly adjusted in the process of Example 21) is overlaid on a substrate 6004 containing metal electrodes 6001 and 6002, optionally prior to electrode deposition by screen printing. Substrate 6004 is a supporting dielectric material with a low coefficient of thermal expansion, such as alumina. After attaching the sheet to the substrate, the entire disc is liquid densified using the process of Example 23. After drying, the film exhibits strong adhesion to the surface. To avoid environmental influences on resistors, nanofiber sheet registers are preferably packaged using the same technology as that of organic light emitting diodes. The register at the time of manufacture has an extremely low temperature coefficient of resistance (α = 7.5 × 10-⁴K^-1) And low 1 / f noise.</p><p num="0626"> Example 56 The present embodiment illustrates the fabrication of screens for electromagnetic shielding (EM) according to some embodiments of the present invention. A schematic example of such an EM shield device is shown in FIG. Optionally, this EM shield screen was attached to the surface using a nanofiber extraction process (Example 21) in a solid state and was shown in Example 23 (using a sheet deposition process as in Example 18). (Using a selective sheet densification process such as), it can be manufactured as a self-supporting transparent sheet. The nanotube orientation can optionally be aligned along the patterning direction of the front transparent electrode of the display screen to obtain an effective EM shield. Alternatively, the EM shield may contain nanotube sheet deposits that are not oriented in the same direction (for the purpose of eliminating the polarization effect on the screen).</p><p num="0627"> Example 57 The present embodiment illustrates the use of highly aligned porous MWNT nanofiber sheets as gas sensor host materials according to some embodiments of the present invention. MWNT itself is not highly sensitive to adsorbed gas. However, the MENT suspension sheet is mechanically tough, porous and highly anisotropic conductivity along and orthogonal to the nanotube arrangement direction. The coefficient of this anisotropy is usually 20 or more, but it can be easily increased to 100 or more by mechanical treatment. SWNTs from the suspension are deposited on the MWNTs to sensitize the MWNTs. (Like the deposition of SWNTs from liquid dispersions) or grow SWNTs on top of MWNTs (by known CVD processes). In one embodiment (exemplified in FIG. 62A), the MWNT sheet is deposited on a dielectric substrate (such as glass or ceramic) with electrodes 6201, 6202, 6203, and 6204 already deposited. In another embodiment, the openings in the substrate allow the porous MWNTs containing the gas-deposited SWNTs to pass through. As a result, the conductivity across MWNTs is determined by the conductivity of the deposited SWNT6206, which is very sensitive to the gas environment as an inherent property. Figure 62B illustrates the high sensitivity of SWNT sheets (HiPco nanotube paper produced by filtration) to vapors of benzene and alcohol. After each gas exposure and measurement cycle, the sensitive surface of the device was along the host MWNT, ie, the MWNT sheet up to 300 ° C, optionally by applying an electric current to electrodes 6201 and 6202 in Figure 62A. It is recovered by heating.</p><p num="0628"> Example 58 The present embodiment illustrates an application in which nanotube sheets and threads are used as antennas, according to some embodiments of the invention. Such an antenna, including the nanotube sheet of Example 21, is transparent and is the case for an antenna based on sparsely weaving the nanotube yarns of the embodiment of the invention into a transparent fabric. Optically transparent antennas can be stacked on top of radio frequency identification (RFID) tags, paintings, optical frames, displays, and other structures that require optical visibility overlaid on barcodes. In some examples, such as those of the above embodiments, the antenna has a structure as shown in FIG. 63, such an antenna comprising a microstripline type feeder. Such a feeder may be a copper line or other conductor strip and may be a transparent material such as another nanofiber sheet or ITO film. In some embodiments, an antenna reflector surface made of a thin insulating layer of 5-10 micron polymer and a single nanofiber sheet is coated on a microstripline type feeder, or for good conductivity. Several sheets with threads are laminated on top. The resonant wavelength of the antenna can be adjusted by the length of the nanofiber element L, which optionally has an average thickness derived from the nanofiber sheet or the nanofiber forest array into which the yarn is spun.</p><p num="0629"> Example 59 This embodiment illustrates an MWNT nanofiber sheet-based heat exchanger. Sheets drawn from MWNT show extremely high thermal diffusivity and thermal conductivity. The densification of the sheets on the substrate dramatically reduces heat transport by double orders of magnitude to improve heat dissipation to the substrate. On the other hand, heat transport along the non-dense sheet remains very high. This embodiment describes the use of MWNT sheets as heat exchangers for computer motherboards. A laptop computer with high electron density distributes and embraces several highly integrated processors on a motherboard. It is not possible for each processor to have a cooling fan that is often used in the main processor of desktop computers. Laptop computers typically use copper heat exchangers to direct all heat to a metal plate, which is cooled by fan coolers built into several corners of the computer body. The thermal diffusivity of MWNT sheets is double orders of magnitude higher than that of bulk copper. To improve heat exchange as shown in FIG. 64, Applicants deliver heat energy by a cooler 6404 incorporated into several corners of the computer body by a copper plate 6403 covered with MWNT sheet 6401. To propose. The upper surface (6402) and fan cooler in contact with the processor (or other heat source) are preferably densified to improve heat exchange between the copper plate and the MWNT sheet. In some cases, the heat transport bus can be undensity.</p><p num="0630"> Example 60 This example shows the field emission characteristics of MWNT twisted yarn studied in a single-ended geometry (Fig. 66B). MWNT yarns with a diameter of 10 μm were obtained using the drawing and plying process of Example 2 and an automated version of this process (as shown in Example 48). One end of a 6 mm long thread was attached to a nickel plate using the conductive tape used for SEM. In this way, a self-supporting 5 mm MWNT yarn was obtained at any angle. The MWNT cathode produced in this way is introduced into a vacuum chamber together with a tungsten anode, and the chamber is 10^-7The vacuum pump was exhausted to the torr. The distance between the nickel plate and the tungsten anode was 10 mm. A short (1ms), high voltage (2000V) tuned pulse was applied to erect the MWNT yarn in a nearly vertical orientation. After that, IV measurement was performed in the DC system. FIG. 67 shows the IV curve for field emission of single-ended geometric yarns. It's easy to see that there are three stages. At low voltage, no current flows other than noise from the measurement system. From 700V to 1200V, field emission appears to follow the Fowler-Nordheim (FN) law (R. Gomer, Field Emission and Field Ionization, Harvard University Press, Cambridge, MA, 1961, 1-2). Above 1200V, the IV curve of field emission deviates significantly from the FN law, which may be due to some current saturation due to the field emission mechanism of adsorbent-enhanced field emission.</p><p num="0631"> Example 61 This embodiment illustrates the light emission of the cathode at the end of a single yarn from a vertical geometry according to some embodiments. Incandescent light emission was observed from the end of the yarn when the applied voltage exceeded 1460 V in the geometric shape of the end of the single yarn (see Fig. 68 insertion). Such release is due to Joule heating. FIG. 68 shows an incandescent light spectrum. Here the temperature is about 2200K based on the color of the emitted light.</p><p num="0632"> Example 62 The present embodiment exemplifies electron emission from a nanofiber thread cathode having a planar geometric structure according to some embodiments of the present invention. From MWNT yarns with a diameter of 10 μm and a length of meters, a 12 mm length section was taken out and both ends were connected to nickel plates with electrically conductive SEM tape. Such a thread of about 10 mm was held uncovered. The prepared sample is introduced into a vacuum chamber with a tungsten anode, the chamber is 10^-7The vacuum pump was exhausted to the torr. The shape of the experiment is shown in Figure 66A. Electron emission characteristics from the sides of the exposed yarn in the 10 mm length section were tested in a DC regime with Keithley 237 units. Figure 69 shows the IV plot for the lateral field emission of the MWNT yarn. A typical IV (current (I) vs. voltage (V)) plot in this shape exhibits hysteresis behavior. The initial (first rise) IV plot is fairly steep and has a threshold electric field (0.9 V / μm) greater than the value observed in subsequent measurements (0.7 V / μm). This hysteresis behavior may be the result of electrostatic forces that clutter the MWNTs on the yarn and thereby fluff. After this, the Fowler-Nordheim plot can be repeated, and it seems that it can be interpreted within the framework of the Fowler-Nordheim theory of cold cathode electron emission. Once a slightly higher electric field on the order of about 5-8 kV for 10-15 hours was applied, the electrostatic fluffy forest further developed nanotube protrusion. This was the result of fluffing on the surface of the MWNT yarn (see Figures 74A and B). The same side geometry was similarly used in the phosphor screen anode instead of the tungsten plate. Typical images of field emission from the yarn in this lateral geometry with a phosphor screen anode are depicted in FIGS. 70 and 71. A negative pulse voltage was applied to the cathode using the HV Pulse M25K-50-N unit to avoid rapid fluorescence burning in the DC regime. The pulse repetition rate was 1 kHz and the load cycle was 1%. It was clearly confirmed that the field emission characteristics of the MWNT yarn were very uniform. Furthermore, at certain applied voltages, the field emission sites were indistinguishable. This property of uniform side emission from MWNT yarn can be widely used for different types of flat panel displays and indicators such as letter and / or symbol code numbers (as shown in Figure 71).</p><p num="0633"> Example 63 The present embodiment describes the use of a transparent MWNT nanofiber sheet as a cold cathode for field emission. The nanotube fiber sheet was adjusted according to Example 21 above, placed on a square glass plate (25 mm × 25 mm, thickness 1 mm) and densified twice in methanol using the densification method of Example 23. Was done. All edges of the nanotube sheet were then covered with SEM conductive tape. As a result, the 10 mm border strip of the sheet was completely covered. An uncovered quadrilateral surface of 5 mm x 5 mm was left. FIG. 79 is a schematic example of a flat cold cathode adjusted in this way. The cathode is introduced into the vacuum chamber with the tungsten anode, 10^-7The pump was exhausted to the tor. The field emission characteristics of the transparent sheet cathodes of uncovered square MWNTs were studied in Keithly 237 units. The distance between the cathode and the tungsten plate anode was 250 μm. The IV plot of the field emission of the MWNT transparent sheet showed that the threshold electric field (when the field emission current reaches 100 nA) is 0.8 V / μm.</p><p num="0634"> Example 64 This example illustrates the application of transparent nanotube sheets for conventional display technology (as in FIG. 82) where the phosphor screen is between the electron emitting element and the observer. The cathode conditioned in the previous embodiment is introduced into a vacuum chamber with a fluorophore anode and the chamber is pumped 10^-7The pump was exhausted to the tor. The fluorescent screen comprises an ITO coated glass coated with "green" TV phosphorus. Cathodic luminescence images were observed through the glass window of the chamber. In this example, the fluorescent screen was installed between the cathode and the chamber glass window (as in the schematic view of FIG. 82). The distance between the cathode and the phosphor screen anode was about 200 μm. A typical image of field emission with a fluorescent screen anode and the cold cathode is a completely non-uniform intensity distribution, probably due to a change in the density of the ends. A negative pulse voltage was applied to the cathode using the HV Pulse M25k-50-N power supply to avoid rapid fluorescence burning in the DC regime. The pulse repetition rate was 1 kHz and the load cycle was 1%. The amplitude of the typical negative pulse applied was between 300V and 3kV.</p><p num="0635"> Example 65 This embodiment illustrates a novel type of display technique or embodiment of the invention in which a transparent nanofiber sheet cathode emitter separates a phosphorescent radiating zone from an observer. A cathode as adjusted in the previous embodiment is introduced into the vacuum chamber with the fluorescent screen above, and the chamber is pumped 10^-7It was exhausted to the tor. The transparent nanotube sheet was installed between the glass window of the cold cathode chamber and the light emitting surface (as shown in FIG. 83). A typical image of field emission from the cold cathode combined with the phosphor screen anode is shown in FIG. The details of the pulse voltage and the power supply used were the same as in Example 64.</p><p num="0636"> Example 66 The present embodiment is provided to illustrate PLEDs on carbon nanotube-based polymer LED devices: flexible plastics, according to some embodiments of the invention. Such a device can comprise the following structure: carbon nanotube (CNT) sheet / PEDOT: PSS / MEH-PPV / calcium / aluminum, similar to the device described in Example 32. Free-standing carbon nanotube (CNT) nanofiber sheets (shown as 8505 in Figure 85) are flexible plastics (potylene terephthalate (PET) or poly (ethylene-2,6-naphthalate (PEN)) to manufacture the above devices. ) Is installed on the substrate. The undensified sheet is weakly bonded to the substrate and can be scraped off very easily. Care must be taken to prevent this from happening during subsequent processing. Then the CNT sheet is placed on top. The provided substrate is densified. The densification is performed by placing the substrate in a beaker of methanol or ethanol. The substrate is gripped vertically and immersed in the solvent along the sheet orientation direction. The substrate is then placed on a cloth and dried. This dipping and drying is performed more than once. The CNT sheet is now densified and has a thickness of about 200 nm. From this densified sheet After the solvent has dried, several layers of hole-injected polymer PEDOT: PSS (denoted as 8504) are deposited. PEDOT: PSS (Bayer) is filtered before depositing on the CNT substrate. The first layer is deposited for 20 seconds at a spin rate of 6100 rpm with an initial acceleration of 21500 rpm / sec. The plastic syringe is filled with an aqueous solution of PEDOT: PPS. Spinning is initiated and the solution is immediately dropped onto the substrate while the acceleration is still ongoing. This forms a thin film of PEDOT: PPS. The substrate is now baked at 120 ° C for 30 minutes. PEDOT: The second layer of PPS is deposited using a spin process with a slower acceleration of 160 rpm / sec, but at the same target speed of 6100 rpm for 20 seconds. However, unlike the first membrane, which started rotating before the solution was dropped, the solution was dropped onto the substrate before the start of spinning. The film is then baked under the conditions of 120 ° C x 30 minutes described above. The third and fourth layers are deposited using the same conditions used for the second layer (6100 rpm, 160 rpm / s acceleration, 20 s). Baking at 120 ° C x 30 minutes after each deposition. The radiation layer (8503 layer) of the device is made from 0.2 wt% MEH-PPV chloroform solution. The MEH-PPV solution is dropped (ie, deposited) on a substrate containing a CNT sheet and a PEDOT: PSS film. Spinning takes place at a speed of 3000 rpm for 30 seconds with an initial acceleration of 3400 rpm / sec. Spinning is initiated and immediately a solution of MEH-PPV / chloroform is dropped from a plastic syringe onto the accelerated substrate. One MEH-PPV membrane is manufactured on the device. The MEH-PPV membrane is then dried overnight in an argon-filled glove box. Device production is shown in Fig. 85 CNT / PEDOT: A cathode is deposited on the PSS / MEH-PPV structure to complete the process. Cathode deposition is performed in a high vacuum chamber with a thermal deposition device. Calcium (8502 in Figure 85) and aluminum (8501) are deposited from the separated sources in a single pump down cycle. The base pressure in the chamber before the start of deposition is &lt;2 x 10^-6Torr. A shadow mask is used to place the cathode in the desired position on the substrate. Calcium is initially deposited at 0.5 Å / sec. After 100 Å of Ca is deposited, the velocity is raised to 2 Å / sec for 60 seconds. This rate is maintained until 300 Å of calcium is deposited. Aluminum (Al) is then deposited at a constant rate of 5 Å / sec until 1200 Å is deposited. The results of the test show the same results as those described in Example 32.</p><p num="0637"> Example 67 This example provides to illustrate carbon nanotube-based low molecular weight OLEDs on display glass or flexible plastics according to embodiments of the present invention. This device is similar to the polymer type device described above, but incorporates a thermally evaporated molecular membrane as the active layer instead of the polymer membrane. The device structure is as follows: Carbon nanotube (CNT) sheet / PEDOT: PSS / α-NPD / Alq as shown in Figure 86.₃/aluminum. To manufacture the device, a self-supporting carbon nanotube (CNT) sheet (8606) is placed on Corning 1737 display glass (8607) or flexible plastic (PET or PEN, 8608). The sheet binds weakly to the substrate and can be scraped off very easily. Care must be taken to prevent this from happening during subsequent processing. Next, the substrate with the CNT sheet on the top is densified. Densification is performed by placing the substrate in a beaker of methanol or ethanol. The substrate is gripped vertically and immersed in a solvent along the sheet orientation direction. The substrate is then placed on the cloth and dried. This dipping and drying is performed more than once. The CNT sheet is then densified and has a thickness of about 200 nm. After the solvent has dried from this densified CNT sheet, several layers of hole-injected polymer PEDOT: PSS (denoted as 8504) are deposited. PEDOT: PSS (Bayer) is filtered before depositing on the CNT substrate. The first layer is deposited for 20 seconds at a spin rate of 6100 rpm with an initial acceleration of 21500 rpm / sec. The plastic syringe is filled with an aqueous solution of PEDOT: PPS. Spinning is initiated and the solution is immediately dropped onto the substrate while the acceleration is still ongoing. This forms a thin film of PEDOT: PPS. The substrate is now baked at 120 ° C for 30 minutes. PEDOT: The second layer of PPS is deposited using a spin process with a slower acceleration of 160 rpm / sec, but at the same target speed of 6100 rpm for 20 seconds. The solution is dropped onto the substrate before the start of spinning. The membrane is then baked at 120 ° C for 30 minutes. The third and fourth layers are deposited using the same conditions used for the second layer (6100 rpm, 160 rpm / s acceleration, 20 s). Baking at 120 ° C x 30 minutes after each deposition. The transport layer (8603) and radiation zone (8604) of the device are manufactured in a high vacuum chamber equipped with a thermal deposition source. Layers are 2x10 boats made of resistant heating tungsten or molybdenum containing organic powder^-6Accumulated at toll-based pressure. The first layer (αNPD, hole transport layer: 8603) is deposited on the existing CNT / PEDOT-PSS layer at a constant rate of 1 Å / sec until it accumulates at 700 Å. Second layer (Alq₃, Radiation and electron transport layer: 8604) is deposited at 1 Å / sec until it accumulates at 500 Å. The chamber is then depressurized and a shadow mask used for cathode deposition is placed on the substrate. The chamber is pumped out again and a two-layer cathode of lithium fluoride and amminium is deposited on top of the structure. The lithium fluoride layer is deposited at a rate of 0.1 Å / sec until a thickness of 10 Å is accumulated. The last layer of aluminum is initially deposited at 0.2 Å / sec. Once 100 Å is deposited, the speed is raised to 5 Å / sec for 60 seconds. This rate is maintained until 1200 Å of aluminum is deposited.</p><p num="0638"> Example 68 This embodiment is provided to illustrate carbon nanotube-based PLEDs with a bottom-up structure for constructing drive electronics for active matrices, as shown in FIGS. 87 and 88. The device structure is as follows: Aluminum / Calcium / MEH-PPV / PEDOT: PSS / CNT sheet. Manufacture of the device begins with the display glass 8706 layer of FIG. 87 or n-type silicon (8806 of FIG. 88). The substrate is placed on a shadow mask and placed in a vacuum chamber with a source of tungsten or molybdenum for the thermally evaporative metal. For the fabrication of the bottom-up OLED of Figure 87, an aluminum layer (8705) is deposited at a rate of 5 Å / sec until a final thickness of 1000 Å is obtained. A 300 Å thick calcium layer (8704) is then deposited at a similar rate of 5 Å / sec. The metal coated substrate is moved directly from the vacuum chamber into an inert atmosphere to prevent the calcium membrane from being exposed to oxygen. The MEH-PPV membrane (8703) is spin cast onto the substrate from a 0.2 wt% MEH-PPV chloroform solution while confined in an inert atmosphere. A syringe is used to drop the solution onto the accelerating spinner. A 30 second duration is used at a spin rate of 3000 rpm with an acceleration of 3400 rpm / sec to deposit the membrane. The membrane is dried overnight before subsequent membrane deposition. After drying the membrane, several layers of PEDOT: PSS are added (8702). The first layer is started with a spinner accelerating at about 160 rpm / sec and is immediately deposited by dropping the solution from the syringe onto the substrate. The target velocity is 6100 rpm and the duration of deposition is 20 seconds. Subsequent layers use the same spinning parameters, but the solution is dropped onto the substrate before spinning the spinner. After each membrane is deposited, it is baked at 120 ° C for 30 minutes. Al / Ca / MEH-PPV / PEDOT: for the final step of device manufacturing The substrate with PSS is placed on a stand and a self-supporting nanotube sheet (8701) is placed on top of the existing membrane. The sheet is then weakly bonded to the substrate. The entire substrate is immersed in an ethanol or methanol beaker with an immersion that is held vertically and moved in the same direction as the orientation of the nanotube sheet. This is repeated several times, drying the solvent between each immersion.</p><p num="0639"> Example 69 This embodiment is provided to illustrate a essentially transparent PLED based on the use of carbon nanotube sheets as shown in FIG. 89 for both anodes and cathodes. The nanotube anode is placed on the display glass or flexible plastic according to some embodiments of the present invention. Such devices have the following structure: CNT sheet / PEDOT: PPS / MEH-PPV / calcium coated CNT sheet. To manufacture the device, a self-supporting carbon nanotube (CNT) sheet (8904) is placed on Corning 1737 display glass (8905) or flexible plastic (such as PET or PEN). The sheet has a weak substrate and can be scraped off very easily. Care must be taken to prevent this from happening during subsequent processing. Next, the substrate with the CNT sheet on the top is densified. Densification is performed by placing the substrate in a beaker of methanol or ethanol. The substrate is gripped vertically and immersed in the solvent along the sheet orientation direction. The substrate is then placed on the cloth and dried. This dipping and drying is performed more than once. The CNT sheet is then densified and has a thickness of about 200 nm. After the solvent has dried from this densified sheet, several layers of the hole-injected polymer PEDOT: PSS (8903) are deposited. PEDOT: PSS (Bayer) is filtered before depositing on the CNT substrate. The first layer is deposited for 20 seconds at a spin rate of 6100 rpm (with an initial acceleration of 21500 rpm / sec). The plastic syringe is filled with an aqueous solution of PEDOT: PPS. Spinning is initiated and the solution is immediately dropped onto the substrate while the acceleration is still ongoing. This forms a thin film of PEDOT: PPS, which has the function of giving the substrate increased adhesion of CNT sheets. The substrate is then baked at 120 ° C for 30 minutes. PEDOT: The second layer of PPS is deposited using a spin process with a slower acceleration of 160 rpm / sec, but at the same target speed of 6100 rpm for 20 seconds. However, unlike the first membrane, which started rotating before the solution was dropped, the solution was dropped onto the substrate before the start of spinning. The membrane is then baked at 120 ° C for 30 minutes. The third and fourth layers are deposited using the same conditions used for the second layer (6100 rpm, 160 rpm / s acceleration, 20 s). Baking at 120 ° C x 30 minutes after each deposition. Before adding the radiation layer (8902), it is necessary to coat the self-supporting CNT sheet with calcium. This is done in a vacuum chamber with tungsten or molybdenum as the metal evaporative source. The chamber is &lt;2 x 10^-6Pumped to the base pressure of the torr, the calcium layer is deposited at 1 Å / sec until it is deposited to a thickness of 300 Å. The radiative zone (8902) of the device is made by dropping casting onto a substrate using a syringe with 0.15 wt% MEH-PPV solution. Instead of spinning the membrane, the substrate can be tilted vertically to allow excess solution to flow onto an absorbent, dust-free clean room cloth. The substrate is placed horizontally again and the free-standing CNT sheet (8901) is placed on the calcium side of the membrane while the coated material is still moist. It is dried overnight in an inert atmosphere. After drying, the CNT nanofiber sheet (8901) is densified in an inert atmosphere using a methanol or ethanol solution containing a very low concentration of MEH-PPV. The substrate is dropped vertically along the arrangement direction of the CNT sheet. After a few hours of drying, the solvent is removed and the device is ready for use.</p><p num="0640"> Example 70 Figure 90 depicts an organic solar cell or photodetector based on an nanotube ribbon with a carbon nanotube ribbon on the front surface as a transparent conductive electrode. As seen in FIG. 90, the organic solar cell or photodetector can be formed on the glass substrate 9005. First, the aluminum electrode 9004 is deposited on the glass substrate. An ITO-coated glass substrate (~ 85% light transmittance &lt;15 ohms / ) was obtained from Delta Technologies. EL-grade PEDOT-PSS was purchased from Bayer. RR-P3HT and PCBM were purchased from American Dye Source. All materials were used as received without further purification. Applicants have ~ 9mm on each substrate²We made four devices with the area of. The ITO coated glass substrate was pre-etched and purified by plasma treatment (90 seconds for a flexible substrate) under oxygen gas for 5 minutes. A layer of PEDOT: PSS 9003 was then spin-coated on the substrate at 6100 rpm to create a 30-35 nm layer, and the sample was dried by heating at ~ 120 ° C for 100 minutes (60 minutes at 110 ° C for the film substrate). ). The photoactive material was dispersed in a magnetic stirrer for 3-7 days until optimally dispersed. Using a toluene solution consisting of about 1: 2 ratio of PCBM and RR-P3HT, the solution was spin coated onto the sample at 700 rpm to create a 50-60 nm layer. The final layer was layer 9002 consisting of 65% RR-P3HT and 35% PCBM. Carbon nanotube ribbon 9001 was then deposited. Surface Profiler (AMBIOS XP-1) was used to measure the film thickness. The final device was then annealed on a hot plate in the glove box at the desired temperature for the desired time. An organic semiconductor or a mixture of organic p-type and n-type semiconductors was deposited on this electrode. The solar cell was completed by applying a sheet of carbon nanotube nanofibers. In some cases, the nanotube sheet can be densified using the surface tension effect of the absorbed liquid. The rapid evaporation of the solvent absorbed into the sheet causes the sheet to shrink in the thickness direction, which results in densification.</p><p num="0641"> Example 71 As shown in FIG. 90, an organic solar cell or photodetector is formed on a plastic substrate (polyethylene naphthalate or polyethylene terephthalate) according to an embodiment of the present invention as in Example 70.</p><p num="0642"> Example 72 FIG. 91 shows a solar cell or photodetector based on a carbon nanotube ribbon as a bottom transparent conductive electrode on a glass substrate. The first aligned carbon nanotube sheet 9104 is deposited on the glass substrate. An enlarged SEM image of the aligned carbon nanotube sheets 9104 is shown on the left side of FIG. The nanotube sheet is optionally densified using the surface tension effect of the absorbed liquid. Rapid solvent evaporation in the sheet causes shrinkage in the thickness direction, leading to higher densities. PEDOT: PSS9103 was then spin-coated on the surface at 6100 rpm to create 30-35 nm. The sample was dried by heating in a glove box at ~ 120 ° C for 100 minutes (for film substrate, at 110 ° C for 60 minutes). An organic semiconductor or a mixture of organic p-type and n-type semiconductors 9102 was deposited on this electrode as in Example 70. The solar cell was completed with the application of aluminum electrode 9101 (typically thermal vacuum deposition).</p><p num="0643"> Example 73 The present embodiment illustrates a solar cell or photodetector based on a carbon nanotube ribbon as a bottom transparent conductive electrode on a flexible plastic substrate (polyethylene naphthalate or polyethylene terephthalate) as in Example 72. give away. First aligned carbon nanotube sheets are deposited on the glass substrate. The nanotube sheet is more densified by the surface tension effect of the absorbed liquid (as described above). Rapid solvent evaporation in the sheet causes shrinkage in the thickness direction, leading to higher densities. An organic semiconductor or a mixture of organic p-type and n-type semiconductors was deposited on this electrode as in Example 70. Solar cells were completed by applying aluminum electrodes (typically thermal vacuum deposition).</p><p num="0644"> Example 74 The present embodiment provides exemplifying the fabrication of a transparent solar cell with two transparent CNT sheets according to some embodiments of the present invention. FIG. 92 illustrates a solar cell or photodetector based on a ribbon / sheet of carbon nanotubes as transparent conductive electrodes at the top and bottom. First, the carbon nanotube sheet 9204 is deposited on a solid glass or flexible plastic substrate. Nanotube sheets are densified using the surface tension effect of more absorbed liquids. Rapid solvent evaporation in the sheet causes shrinkage in the thickness direction, leading to higher densities. A very thin Al layer 9203 (&lt;100 nm) is then deposited on top of the CNT sheet. An organic semiconductor or a mixture of organic p-type and n-type semiconductors 9202 is deposited on this Al-coated electrode. The active organic layer is transparent because the organic layer is thin. The transparent device is completed by applying the carbon nanotube sheet 9201. Nanotube sheets are densified using the surface tension effect of more absorbed liquids. Rapid solvent evaporation in the sheet causes shrinkage in the thickness direction, leading to higher densities. Transparent solar cells can be used, for example, in smart windows or smart multifunction ceilings or building covers.</p><p num="0645"> Example 75 FIG. 93 illustrates a connected solar cell or photodetector based on a carbon nanotube ribbon / sheet as the upper transparent conductive electrode. First, a bottom reflective aluminum electrode 9302 is deposited on the substrate 9301. An organic semiconductor or a mixture of organic p-type and n-type semiconductors 9303 is deposited on this electrode. The first solar cell is completed by applying a carbon nanotube sheet 9304 as a transparent separation layer (also called a charge recombination layer). Nanotube sheets are densified using the surface tension effect of more absorbed liquids. Rapid solvent evaporation in the sheet causes shrinkage in the thickness direction, leading to higher densities. A thin alumnium layer 9305 can optionally be deposited on the nanotube sheet electrodes to reduce voltage loss prior to application of the first cell. A second organic semiconductor layer or organic p-type and n-type semiconductor mixture 9306 is deposited on this electrode. The articulated solar cell is completed by applying the carbon nanotube sheet 9307. Again, such nanotube sheets are optionally densified using the surface tension effect of the absorbed liquid.</p><p num="0646"> Example 76 This example illustrates the additional functionality of carbon nanotubes for charge collectors for enhanced light absorption in solar cells and charge generation and nanoantenna effects by three-dimensional structure (Fig. 94). The large interface and nanoscale morphology between organic materials and carbon nanotubes significantly improves photoinduced charge transfer, charge separation and capture. This is an experimental fact that the spectral sensitivity is increased by the additional photo-induced charge transfer between the organic material and the carbon nanotubes (Fig. 94). The nature of the spread and aligned CNT sheets can improve the morphology between the donor and acceptor materials and extend the spectral sensitivity down to the infrared range. Due to the simplification selection rule, it is well known that localized plasmon excitation by direct light absorption can occur in small metal nanoparticles. Excited plasmons can lead to an increase in the amount of photoexcited electrons in a metal that can overcome the Schottky barrier. Carbon nanotubes modified with metal nanoparticles were tested for this purpose. High field strength near the excited surface plasmon can also lead to increased absorption of photons in the organic matrix. Therefore, the surface plasmon effect can lead to an increase in photocurrent in the organic solar cell in the spectral region where the organic material does not absorb much. Plasmon excitation in carbon nanotubes and metal coated nanofibers can increase the UV spectral sensitivity of CNT-based solar cells and photodetectors. Absorption spectra were measured with a Perkin Elmer Lambda 900 UV-Vis-NIR spectrophotometer. Current-voltage characteristics were recorded with the Keithley 236 source measure unit. Solar simulator (150W xenon lamp with AM0 and AM1.5 filters from Spectra-physics and focus lens) 100mW / cm²Light intensity calibrated at and used as a light source for solar cell efficiency measurements. The reported efficiency measurements were not corrected due to spectral mismatch.</p><p num="0647"> Example 77 This example shows a transparent carbon nanotube sheet embedded in a polarization sensitive detector. The high anisotropy of the aligned CNT sheets makes it possible to increase the polarization ratio by 25% as shown by the IV curve in Figure 97. The broadband (300 nm-10 μm) polarization sensitive detector comprises a carbon nanotube ribbon / sheet as a transparent polarized conductive electrode on top and an aluminum bottom electrode deposited on a glass or plastic substrate. An organic semiconductor or a mixture of organic p-type and n-type semiconductors is deposited on this electrode. A high degree of polarization ratio is achieved by mechanical rubbing of the organic layer or other means (eg, field alignment). Solar cells are completed by applying carbon nanotube sheets. Nanotube sheets are densified using the surface tension effect of more absorbed liquids. Rapid solvent evaporation in the sheet causes shrinkage in the thickness direction, leading to higher densities. The degree of polarization ratio can be additionally increased by placing an additional CNT sheet on the Al bottom electrode to polarize the light reflected back from the Al electrode.</p><p num="0648"> Example 78 This example shows a method of improving the electrical conductivity and adjusting the work function of carbon nanotubes by depositing a thin film of a metal having a large work function such as Au and Pt on a carbon sheet as shown in FIG. 98. Sheet resistance can be reduced to at least 1/5 of 100 ohms / . The self-supporting CNT sheet can be used as an anode for solar cells due to its high work function metal coating such as Au and Pt. FIG. 98 shows an SEM image of an Au / Pd coated carbon nanotube sheet.</p><p num="0649"> Example 79 This example shows a method of depositing a thin film of a metal having a low work function such as Al or Ca on such a carbon sheet to adjust the work function of the carbon nanotube sheet and improve electrical conductivity. Sheet resistance can be reduced to at least 1/5 of 100 ohms / . The low work function metal coating such as Al or Ca allows the self-supporting CNTs to be used as cathodes for solar cells.</p><p num="0650"> Example 80 In some embodiments, the present invention is widely applicable to thin transparent organic or optical transistors, which include a CNT sheet electrode, a thin transparent undergate insulator (inorganic or organic) and an organic photoactive layer, display. And can be used to make various transparent integrated circuits, including those for light detectors. Figure 99 depicts a transparent optical transistor based on a carbon nanotube ribbon / sheet as a bottom transparent conductive electrode. First, the transparent CNT sheet electrode 9902 at the bottom is deposited on the substrate 9901. SiO₂Or Al₂O₃Alternatively, a polymer insulator such as parylene is coated on top of the gate dielectric 9903. Formed by placing two transparent carbon nanotube ribbons on top of the source 9904 and drain electrode 9905 insulating layers. A transparent optical transistor is completed by depositing an organic semiconductor or an organic p-type and n-type semiconductor mixture 9906 on top of the structure. Nanotube sheets are densified using the surface tension effect of more absorbed liquids. Evaporation of the solvent in the sheet causes shrinkage in the thickness direction, leading to high density. The transparency of this device allows for optical regulation of source-drain currents, helping to transfer information from optical chip to chip.</p><p num="0651"> Example 81 The present embodiment is provided to illustrate the preparation of transparent nanofiber-metal oxide photoelectrodes according to some embodiments of the present invention. The transparent nanotube sheets produced by the processes of Examples 18 and 21 were deposited as sheet deposits arranged on a glass substrate. The electrical and optical properties are anisotropic due to the well-arranged nanotubes in the sheet. A transparent and porous nanofiber electrode 10102 was made according to the present invention with reference to FIG. Metal oxide nanoparticles (eg 10-20nm TiO)₂The semiconductor photoelectrode 10103 containing nanoparticles) was coated by printing or sol-gel on the rough surface of the transparent porous nanofiber electrode 10102 to form a film about 10-20 μm thick. Sintering and formation of the anatase phase was performed for 30-60 minutes in an inert atmosphere at 450 ° C. After sintering, the layer exhibits a porosity of 0.5-0.6. A monolayer of red dye was incorporated into a highly porous nanofiber-metal oxide electrode by impregnation. For example, ruthenium dye-II cis-dithiocyanate-N, N'-bis (2,2'-bipyridyl-4,4'-dicarboxylic acid)-(H₂) (TBA)₂RuL₂(NCS)₂(H₂O)₄The sensitizer was made in absolute ethanol solution at a concentration of 20 mg per 100 ml solution. The impregnation process was run overnight. The electrodes were washed with ethanol and then dried.</p><p num="0652"> Example 82 The present embodiment provides an example of the preparation of a transparent nanofiber-metal oxide photoelectrode by microwave irradiation according to some embodiments of the present invention. A transparent porous nanofiber electrode 10102 was made according to Example 81 on a plastic substrate with reference to FIG. 101. Metal oxide nanoparticles (eg 10-20nm TiO)₂The semiconductor photoelectrode 10103 containing nanoparticles) was coated by printing or sol-gel on the rough surface of the transparent porous nanofiber electrode 10102 to form a film about 10-20 μm thick. Rapid sintering and anatase phase formation were performed with multimode microwave heating and the frequency was 5 minutes at an output of about 1 kW, choosing from a variation range of 2-30 GHz. After sintering, the layer exhibits a porosity of 0.5-0.6. A monolayer of red dye was incorporated by impregnation into the surface of a highly porous nanofiber-metal oxide electrode. For example, ruthenium dye-II cis-dithiocyanate-N, N'-bis (2,2'-bipyridyl-4,4'-dicarboxylic acid)-(H₂) (TBA)₂RuL₂(NCS)₂(H₂O)₄The sensitizer was made in absolute ethanol solution at a concentration of 20 mg per 100 ml solution. The impregnation process was run overnight. The electrodes were washed with ethanol and then dried.</p><p num="0653"> Example 83 The present embodiment provides an example of the preparation of a nanofiber reducing electrode according to some embodiments of the present invention. The transparent porous reducing electrode 10105 of FIG. 101 was manufactured according to an embodiment of the present invention. There is no need to platinum the counter electrode. That is because nanofibers function as both charge collecting electrodes and catalysts.</p><p num="0654"> Example 84 The present embodiment provides an example of the adjustment of a dye-sensitized solar cell according to some embodiments of the present invention. Dye-sensitized solar cells are conditioned by the use of semiconductor photoelectrodes and reduction electrodes of the nanofiber sheets obtained in Examples 81-82. These two electrodes use spacers to maintain the separation between the electrodes at 50-100 μm. A charge conductor is introduced into the space between these two electrodes and sealed. The charge conductor may be a redox pair in a liquid. The following oxidation-reduction electric field qualities are included: (1) TG-50 iodolite (Solaronix); (2) meroxypropionitrile-based material with low viscosity and low boiling point (bp163-165 ° C); 3) Similarly low viscosity but high boiling point (bp 206 ° C) based on γ-butyrolactone, or pseudo solid state electrolyte, or solid state positive such as conjugate polymer (such as poly (3-hexylthiophene)) Pore conductors, or solid-state hole conductors expressing organic low molecular weight substances such as TPD. Electrons generated from photosensitizers or quantum dots can be easily transferred to external circuits using highly conductive nanoporous nanofiber sheets containing three-dimensionally distributed nanofibers. .. Selectively, the carbon nanofiber sheet of the present invention is preferable. In addition, the electrodes can be made flexible and lightweight by using a thin, flexible and transparent substrate. Such solar cells can be used in portable devices.</p><p num="0655"> Example 85 The present embodiment provides an example of the preparation of a transparent dye-sensitized solar cell (DSC) according to some embodiments of the present invention. Dye-sensitized solar cells are conditioned using transparent semiconductor photoelectrodes and transparent redox electrodes obtained from Examples 81-83. Due to having a transparent DSC, the thickness of the upper photoelectrode is limited to 10 μm. Multi-walled carbon nanotube nanofiber ribbon / sheet thickness is limited to 1-2 layers. Both electrodes are spaced 10-100 μm apart by spacers. The charge conductor was introduced and sealed in the space between the two electrodes. The charge conductor may be a redox pair in a liquid. The following oxidation-reduction electric field qualities are included: (1) TG-50 iodolite (Solaronix); (2) meroxypropionitrile-based material with low viscosity and low boiling point (bp163-165 ° C); 3) Similarly low viscosity but high boiling point (bp 206 ° C) based on γ-butyrolactone, or pseudo solid state electrolyte, or solid state positive such as conjugate polymer (such as poly (3-hexylthiophene)) Pore conductors, or solid-state hole conductors expressing organic low molecular weight substances such as TPD. Electrons generated from photosensitizers or quantum dots can be more easily transferred to external circuits using three-dimensionally distributed nanofibers. Selectively, the carbon nanofiber sheet of the present invention is preferable. In addition, the electrodes can be flexible and lightweight using a thin, flexible and transparent substrate. Such solar cells can be used in portable devices.</p><p num="0656"> Example 86 According to this embodiment, the performance of the dye-sensitized solar cell (DSC) is improved by the catalytic electrochemical properties of the single-walled nanotubes by coating the transparent anode made of the transparent sheet of the multi-walled nanotubes of the present invention with the single-walled nanotubes. It is illustrated that it can be done (see SEM image of such electrodes in Figure 102). Applicants show that this process enhances electrochemical charge transfer of holes to SWNT-coated anodes. This example also describes how to make a photoelectrochemical device, a composite nanotube sheet that is an effective anode for a Graetzel battery. Ruthenium Dye-II Sith-Dithiosianate-N, N'-Bis (2,2'-Bipyridyl-4,4'-Dicarboxylic Acid)-(H₂) (TBA)₂RuL₂(NCS)₂(H₂O)₄(Dyesol, B2 / N719) is TiO₂Used as a particle sensitizer. The prepared solution is absolute ethanol (CH)₂CH₂3 × 10 in OH)^-4 It was an M Ru (II) dye. The chemical formula of the dye is RuC₅₈H₈₆N₈O₈S₂. 4H₂It is O. The electrolyte was an iodide-based redox electrolyte-iodolyte TG-50 (from "Solaronix"). Porous titania coated with a conductive substrate, TiO₂(From "Dyesol"), Fluorine Doping SnO₂An overlay, with a transmittance of&gt; 85%, was used as the light electrode in the DSC battery assembly. TiO₂It was sintered at 450 ° C for 30 minutes before sensitizing. Annealed membrane is 3x10 containing ethanol solution^-4 The M Ru (II) dye was immersed overnight (~ 12 hours) at room temperature. TiO₂The electrode was immersed while it was still hot (ie its temperature was about 80 ° C). After the dye adsorption is completed, the electrode is N₂It was dried in the air stream. A typical electrolyte is iodolite TG-50 (from Solaronix), but other electrolytes have also been tested. The counter electrode was tuned with an aligned multi-walled carbon nanotube (MWNT) sheet on a glass substrate. A three-step process was deposited on the top of the sheet with a dispersion of single layer nanotubes (SWNT): (i) Vacuum filtration (filtration) of a dilute, surfactant-based suspension of nanotubes purified on a filtration membrane. A homogeneous film is formed on the film); (ii) Wash the surfactant with pure water; and (iii) Dissolve the filter film in a solvent. Soluble filters were obtained from Millipore (GS-0.22). Approximately 0.3 mg of SWNT (Carbon Nanotechnology) in 100 ml of surfactant (Triton-1000) to make a dispersion of SWNTs HiPco) was used. 3 ml of SWNT dispersion was added to 500 ml of deionized water to make nanotube ink. When the required materials were adjusted, the light and opposite electrodes were placed together offset from each other. The strip of each electrode served as a contact point. Two binder clips were used to hold the electrodes together.</p><p num="0657"> Example 87 This example shows that the performance of the DSC can be further increased by using a large number of nanotube sheets: the measurements show the Dentsu Density-Voltage characteristics of the MENT sheet obtained when ITO alone is used as the counter electrode. Shows that it is comparable to the characteristics. MWNT sheets act as electrochemical catalysts, but are less efficient than regular ITO-based DSCs due to the high series resistance of very thin electrodes. However, when the number of MWNT sheets was increased, the measurements showed high electrochemical activity in the redox electrolyte system, and the short circuit current (I)._SC) Increases with the number of MWNT seats. The contact area between the electrolyte and MWNT increases due to the increase in the number of layers. In addition, the series resistance of the electrodes is reduced.</p><p num="0658"> Example 88 The present embodiment provides an example of adjusting a coupled solar cell according to some embodiments of the present invention. FIG. 103 shows a multi-coupled solar cell (or articulated solar cell), in which the upper transparent electrode is drawn with 10301 and the transparent separation layer 10304 is a single-coupled solar cell layer with visible light spectrum selectivity ( It is located between cell 1, part 10301-10304) and the near-infrared selective part of the solar light spectrum (cell 2, part 10304-10308). The concatenated solar cell comprises two compartment batteries. The upper compartment is a dye or quantum dot sensitized solar cell, adjusted as described in Example 83. The porous metal oxide layer 10302 in the first compartment contains nanoparticles with an average diameter of 10-20 nm. Red dye molecule 10308 ruthenium dye-II cis-dithiosianate-N, N'-bis (2,2'-bipyridyl-4,4'-dicarboxylic acid) on the surface of highly porous nanofiber metal oxide electrode )-(H₂) (TBA)₂RuL₂(NCS)₂(H₂O)₄Monolayer is, for example, RuC₅₈H₈₆N₈O₈S₂. 4H₂Adhered by impregnation with an ethanol solution of O. The porous layer 10302 is then impregnated with a redox electrolyte. The two compartments are separated by a transparent electrically conductive nanofiber sheet 10304 embedded with a transparent non-porous metal oxide matrix. This transparent separation electrode has a transmittance of at least 70% in the region of interest. The second compartment is an infrared quantum dot sensitized solar cell adjusted by the method described in Example 83. The porous metal oxide layer 10305 in the second compartment contains nanoparticles with an average diameter of 50-300 nm. An infrared quantum dot sensitized monolayer is attached to the surface of a highly porous nanofiber metal oxide electrode, which is impregnated with a hexane solution or by in-situ quantum dot growth inside the pores of the metal oxide. Will be done. Examples of the infrared amount dot sensitizer include semiconductor nanocrystals having a charge multiplexing property of PbSe or PbS. The porous layer is then impregnated with redox electrolyte 10306.</p><p num="0659"> Example 89 The present embodiment provides an example of the preparation of a connected solar cell with a double-seat charge separation layer according to some embodiments of the present invention. The dye-sensitized articulated solar potential was adjusted with the semiconductor photoelectrode and reduction electrode obtained in Example 88. The charge separation layer of the double sheet in the connection is a p-type (high work function) transparent nanotube sheet facing the first junction, while an n-type (low work function) nanotube sheet coated on the first junction. Functions as a layer that collects electrons from the second junction. The work function regulation and electrical conductivity of the charge separation layer in the connection is achieved by the deposition of a thin film of gold Au (50 nm) on the carbon sheet on one side (it reduces the sheet resistance to 1/5 of 100 ohms / ). (Decreases), and the other side is coated with a metal with a low work function (such as Al or Ca).</p><p num="0660"> Example 90 In this example, the elastically deformable nanotube sheet can be produced by the process of Example 32, and the nanotube sheet can be elastically deformed without creating a significant dependence of the nanotube sheet resistance on the elongation of the nanotube sheet. It is shown that it is overcoated with a second elastic silicone rubber sheet while maintaining its performance. The importance of this illustration is that it is possible to fabricate deposits of high strain actuators containing one or more layers of working material (such as electrostrained rubber such as silicone rubber) and two or more electrodes. After making the elastic nanotube sheet with silicone rubber of Example 32, the elongation is relaxed, and the second silicone rubber sheet is obtained by liquid-coating the carbon nanotube sheet with silicone rubber resin and then curing the silicone liquid resin. Adhere to the top of the carbon nanotube sheet. After this process (to produce an elastically deformable nanotube sheet between two silicone rubber sheets), we found that the nanotube sheet (and the accompanying silicone rubber sheet) had the resistance value of the nanotube sheet. We have found that it can be highly stretched without causing significant changes. This process can be suitably extended to the production of elastically deformable deposits containing one or more nanotube sheet electrodes between elastic sheets, and the number of alternating nanotube sheet electrodes and elastic sheet electrodes can be of any size. That's right. The methods of this example and 32 can be used to produce an inflatable balloon comprising one or more conductive nanotube sheets. To initiate the process of conducting conductive balloon formation, the initial inner balloon layer can be expanded, optionally using gas or liquid or in the uninflated state on the mandrel, followed by the application of the first nanotube sheet. The expansion can be released before.</p><p num="0661"> Example 91 This example describes a flexible and / or elastic transparent antenna schematically shown in FIG. Such antennas can optionally be manufactured by stacking insulating substrates with the following rigid or flexible (and / or elastic) components: remote feeders in the form of microstrip lines. Such feeders can be manufactured with transparent, oriented nanofiber ribbons separated by a thin insulating layer and placed beneath the radiator / receiver layer and laminated on a flexible or elastic material. Such antennas in receiving mode can be used in radio frequency identification (RFID) systems. The nanofiber-based antenna may be transparent, reflecting the transparency of the nanofiber sheet of the embodiments of the present invention. This transparency allows, for example, to read the barcode underneath along with the tag. The components and components of the device are shown in Figure 63. The antenna component 6301 is composed of a substrate 6301, an aligned nanotube radiator / receiver, a plate 6302 and an array feeder 6303 of a sheet or thread of nanotubes, and a thin insulating separation layer 6304. The patterning of sheet 6302 makes it possible to adjust the frequency of the antenna. Optionally, such elastic antennas can be manufactured in one uniform size and then extended to obtain the desired size and desired antenna characteristics.</p><p num="0662"> All patents and publications referenced herein are incorporated for reference. Since the invention is described in this way, it is clear that the same can be changed to many schemes. Such modifications are not considered to deviate from the gist and scope of the invention, and all such modifications are intended to be within the scope of the claims set forth below, as will be apparent to those skilled in the art. Has been done.</p>