Polymer-inorganic particle composites

Polymer-inorganic particle composite

[0001] This application is a divisional case of an invention patent with an application date of January 23, 2002, an application number of 02806299.X (PCT/US2002/002054), and the title of "polymer-inorganic particle composite material" please.

[0002] Background of the Invention

[0003] The present invention relates to a composite material combining inorganic particles and polymers. The invention further relates to inorganic particles that can be functionalized to produce chemical bonds with other compounds, especially polymers.

[0004] The continuous development of many fields has great demand for many kinds of new materials. In particular, various chemical powders can be used in many different processing situations. In particular, it may be used without machine powder manufacturing an electronic device (e.g., flat panel displays), electronic circuitry and optical and electro-optical material.

[0005] Similarly, technological progress has increasingly demanded improved material processing with strict tolerances for processing parameters. With further miniaturization, the material parameters need to be reduced to a stricter tolerance range. Today's integrated circuit technology has required submicron tolerances for processing dimensions. Self-assembly methods have been developed to provide alternative methods for coating very thin films. However, the self-assembly method is generally limited by the types of materials that can be deposited by a specific method.

[0006] The combination or integration of mechanical components, electronic components, and optical components into a complete device has created further requirements for material processing. Therefore, there is considerable interest in forming specific compositions that can be applied to substrates to perform specific functions. In order to form optical devices with high-quality optical coatings from these materials, the coating must have a high degree of uniformity.

[0007] Composite materials can be used to combine the desired properties of different materials to obtain modified materials. Or, it is possible to form a composite material that can obtain modified or easier-to-control processing characteristics related to one material while having the desired properties of another material. Therefore, in the composite material, according to the processing characteristics provided by another component in the composite material, the desired properties of one material can be incorporated into multiple structures. Composite materials used in certain applications must have a stable structure.

[0008] Summary of the invention

[0009] The first aspect of the present invention relates to a composite material composition containing a polymer having pendant groups that are chemically bonded to inorganic particles. Polymers broadly include oligomers.

[0010] Another aspect of the present invention relates to a composite material containing inorganic particles chemically bonded to a polymer through a bond (which contains a variety of functional groups), the polymer is selected from polyamide, polycarbonate, poly Imide, polyphosphazene, polyurethane, polyacrylate, polyacrylamide, heterocyclic polymer, polysiloxane, polypropylene cyanine, polyacrylic acid, polyvinyl alcohol, polyvinyl chloride, conjugate Polymers, aromatic polymers, conductive polymers and their mixtures. These polymers have functional side groups and/or terminal positions that can be chemically bonded to the inorganic particles, and the inorganic particles can usually be functionalized by bonding with a linking compound.

[0011] The present invention also relates to a composite material composition containing chemically bonded inorganic particles and a polymer, the polymer is selected from polyamide, polycarbonate, polyimide, polyphosphoridine, polyurethane , Polyacrylate, polyacrylamide, heterocyclic polymer, polysiloxane, polypropylene laurel, polyacrylic acid, polyvinyl alcohol, polyvinyl chloride, conjugated polymer, aromatic polymer, conductive polymer and Their mixture. These polymers can chemically bond with inorganic particles at the end positions of their polymer chains.

[0012] Yet another aspect of the present invention relates to a composite material composition containing a polymer chemically bonded to inorganic particles, wherein the inorganic particles include a metal.

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[0013] In addition, the present invention relates to a metal/metalloid oxide or a collection of metal/metalloid nitride particles that can be chemically bonded by a chemical bond, the chemical bond including an amino group, an amide group, and a sulfide group, Disulfide group, alkoxy group, ester group, acid group. They can be chemically bonded to polymers.

[0014] Moreover, the present invention relates to a composite material composition containing chemically bonded inorganic particles and a blend of different polymers.

[0015] Yet another aspect of the present invention relates to a structure comprising a surface and a composite material located within a boundary on the surface. The composite material contains inorganic particles bonded to the polymer.

[0016] Other aspects of the present invention relate to a method of forming a chemically bonded polymer-inorganic particle composite. The method includes bonding a side chain functional group of a polymer unit to a functional group of a linking compound that is bonded to the inorganic particle.

[0017] Another aspect of the present invention relates to an optical device containing a composite material. The composite material contains a polymer and inorganic particles chemically bonded to the polymer.

[0018] Yet another aspect of the present invention relates to a method of forming a device on a solid substrate. The method includes bonding the composite material to the solid substrate. The composite material contains a polymer chemically bonded to inorganic particles.

[0019] The present invention includes:

[0020] 1 A composite material composition, the polymer contained therein has side groups chemically bonded to inorganic particles.

[0021] 2. The composite material composition of item 1, wherein the inorganic particles include metal/metalloid particles, metal/metalloid oxides, metal/metalloid nitrides, metal/metalloid carbides, metal/metalloid sulfides Substances, metal/metalloid phosphates, or mixtures thereof.

[0022] 3. The composite material composition of item 1, wherein the polymer is bonded to the composite material via a side group, and the side group includes an organic part, a siloxy part, a sulfide part, and a sulfate radical. Moiety, phosphate moiety, amine moiety, base moiety, vat moiety, or a combination thereof.

[0023] 4. The composite material composition of item 1, wherein the side groups of the chemical bonding include a sulfonate group, an ester group, a carbonate group, an amide group, an imide group, an amine group, a carbamate group, adenic acid Radical group, acid hexyl group, sulfide group, disulfide group, cinnamyl group, alkoxy group, hydrosilyl group, organosilyl group, silyl group, siloxane group, silazane group, phosphonate group or a combination thereof.

[0024] 5. The composite material composition of item 4, wherein the side group is directly bonded to the inorganic particle at the side group.

[0025] 6. The composite material composition of item 4, wherein the side group is also bonded to one or more carbon atoms through a bond to the inorganic particle.

[0026] 7. The composite material composition of item 1, wherein the side group is bonded to the inorganic particle at a functional group position, and the functional group includes an oxysilyl group, a sulfonate group, a sulfide group, an amine group, a sulfonate group, or Oxo.

[0027] 8. The composite material composition of item 1, wherein the polymer comprises polyamide, polyimide, polyacrylic acid, polyacrylate, polyacrylamide, or polysiloxane.

[0028] 9. The composite material composition of item 1, which has greater than about 6% by weight of inorganic particles.

[0029] 10. The composite material composition of item 1, which has greater than about 25% by weight of inorganic particles.

[0030] 11. The composite material composition of item 1, wherein the average particle size of the inorganic particles is less than about 100 nanometers.

[0031] 12. The composite material composition of item 1, wherein the average particle size of the inorganic particles is less than about 50 nanometers.

[0032] 13. A composite material composition, the inorganic particles contained in it can be chemically bonded to a polymer through a compound containing multiple functional groups, the polymer is selected from polyamide, polycarbonate, polyimide Amine, polyphosphorus cyanine, polyurethane, polyacrylate, polyacrylamide, heterocyclic polymer, polysiloxane, polypropylene cyanine, polyacrylic acid, polyvinyl alcohol, polyvinyl chloride, conjugated polymerization Materials, aromatic polymers, conductive polymers, and mixtures thereof.

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[0033] 14. The composite material composition of item 13, wherein at least one functional group is selected from the group consisting of a sulfonate group, an ester group, an amide group, an imide group, an amine group, a carbamate group, an adenate group, and a carbonate group , Acid sulfide group, sulfide group, disulfide group, blank group, alkoxy group, hydrosilyl group, organosilyl group, silyl group, siloxane group, silazane group, sulfonate group, sulfonate group or Their combination.

[0034] 15. The composite material composition of item 14, wherein at least one of the functional groups is a siloxy group.

[0035] 16. The composite material composition of item 14, wherein at least one of the functional groups is a sulfonium group, an ester group, an amide group, or an acid oxine group.

[0036] 17. The composite material composition of item 14, wherein the particles comprise metal/metalloid oxide, metal/metalloid carbide, metal/metalloid nitride, metal/metalloid sulfide, metal/metalloid phosphoric acid Salt, or their mixture.

[0037] 18. The composite material composition of item 14, wherein the polymer is selected from polyamide, polyimide, polyacrylate, polyacrylic acid, polyacrylamide, polysiloxane, and mixtures thereof.

[0038] 19. The composite material composition of item 14, wherein the polymer comprises a polymer having a conjugated polymer backbone, a polymer having an aromatic polymer backbone, or a mixture thereof.

[0039] 20. The composite material composition of item 14, wherein the polymer comprises a conductive polymer.

[0040] 21. The composite material composition of item 14, wherein the average particle size of the inorganic particles is less than about 500 nanometers.

[0041] 22. The composite material composition of item 14, wherein the average particle size of the inorganic particles is less than about 100 nanometers.

[0042] 23. The composite material composition of item 14, wherein the average particle size of the inorganic particles is less than about 50 nanometers.

[0043] 24. A composite material composition containing chemically bonded inorganic particles and a polymer selected from the following group: polyamide, polycarbonate, polyimide, polyphosphorene, polyurethane Acid esters, heterocyclic polymers, polysiloxanes, polypropylene laurels, polyacrylic acid, polyvinyl alcohol, polyvinyl chloride, conjugated polymers, aromatic polymers, conductive polymers, and mixtures thereof, wherein The polymer is chemically bonded to the inorganic particles through the terminal position of the polymer chain.

[0044] 25. The composite material composition of item 24, wherein the polymer comprises polyamide, polyimide, polycarbonate, polysiloxane, polyurethane, and mixtures thereof.

[0045] 26. A composite material composition in which the polymer contained therein is chemically bonded to inorganic particles, wherein the inorganic particles contain metal.

[0046] 27. The composite material composition of item 26, wherein the composite material has at least about 6 wt% inorganic particles.

[0047] 28. The composite composition of item 26, wherein the metal comprises gold, silver, copper, tongs or rake.

[0048] 29. The composite material composition of item 26, wherein the bond containing multiple functional groups can be chemically combined with the polymer and the inorganic particles.

[0049] 30. The composite material composition of item 26, wherein the sulfide group is bonded to the inorganic particles.

[0050] 31. The composite material composition of item 26 having at least about 25% by weight of inorganic particles.

[0051] 32. A metal/metalloid oxide or metal/metalloid nitride particle assembly that can be chemically bonded by a chemical bond, the chemical bond comprising an amine group, an amide group, a sulfide group, and a disulfide group , Alkoxy group, ester group, acid hydrazine group, and the bond is chemically bonded to the polymer.

[0052] 33. The particle collection of item 32, wherein the particles comprise silicon oxide, silicon nitride or silicon oxynitride.

[0053] 34. The particle collection of item 32, wherein the particles comprise TiO2, zinc oxide, tin oxide or aluminum oxide.

[0054] 35. The particle assembly of item 32, wherein the bond is bonded to the particle via a siloxane functional group, a phosphonate functional group or an oxo functional group.

[0055] 36. A composite material composition containing a blend of chemically bonded inorganic particles and different polymers.

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[0056] 37. The composite composition of item 36, wherein the blend of different polymers comprises an ordered copolymer.

[0057] 38. The composite composition of item 37, wherein the ordered copolymer is a block copolymer.

[0058] 39. The composite material composition of item 38, wherein the block copolymer comprises polystyrene-block-polymethyl methacrylate, polystyrene-block-polyacrylamide, polysiloxane-a Block-polyacrylate/polyacrylic acid, or their mixture.

[0059] 40. The composite composition of item 37, wherein the ordered copolymer comprises a graft copolymer, a comb copolymer, a star block copolymer, a dendritic polymer, or a mixture thereof.

[0060] 41. The composite composition of item 36, wherein the different polymer blend comprises a physical mixture of chemically different polymers.

[0061] 42. The composite material composition of item 36, wherein the inorganic particles are chemically bonded to different polymer subgroups of the different polymer blends.

[0062] 43. The composite material composition of item 36, wherein the composite material is positioned within a confinement on the surface of the substrate.

[0063] 44. The composite material composition of item 36, wherein the inorganic particles comprise metal/metalloid particles, metal/metalloid oxides, metal/metalloid nitrides, metal/metalloid carbides, metal/metalloid sulfides Substances, metal/metalloid phosphates, or mixtures thereof.

[0064] 45. A structure comprising a composite material according to claim 36.

[0065] 46. The structure of item 45, wherein the structure includes fibers.

[0066] 47. The structure of item 45, wherein the structure comprises a thin film.

[0067] 48. The structure of item 46, wherein the inorganic particles are positioned within limits on the film.

[0068] 49. A structure containing a surface and a composite material positioned within a boundary on the surface, and the composite material contains inorganic particles bonded to a polymer.

[0069] 50. The structure of item 49, wherein the structure is a fiber.

[0070] 51. A method of forming a chemically bonded polymer-inorganic particle composite, the method comprising bonding a side chain functional group of a polymer unit to a functional group of a linking compound bonded to the inorganic particle.

[0071] 52. An optical device containing a composite material, the composite material containing a polymer and inorganic particles chemically bonded to the polymer.

[0072] 53. The optical device of item 52, wherein the refractive index of the composite material is at least about 1.8.

[0073] 54. The optical device of item 52, wherein the refractive index of the composite material does not exceed about 1.5.

[0074] 55. The optical device of 52, wherein the composite material contains at least about 5% by weight of inorganic particles.

[0075] 56. The optical device of item 52, which contains a fiber comprising a composite material.

[0076] 57. The optical device of item 52, which comprises a substrate having a thin film containing a composite material.

[0077] 58. A method of forming a device on a solid substrate, the method comprising combining a composite material with the solid substrate, the composite material containing a polymer chemically bonded to the inorganic particles.

[0078] 59. The method of item 58, wherein the composite material is positioned in a specific area on the surface of the solid substrate.

[0079] 60. The method of item 58, wherein the inorganic particles include metal/metalloid particles, metal/metalloid oxides, metal/metalloid nitrides, metal/metalloid carbides, metal/metalloid sulfides, metals / Metal-like phosphates, or their mixtures.

[0080] 61. The method of item 58, wherein the polymer comprises polyamide, polyimide, polyacrylate, polyacrylic acid, polyacrylamide, polysiloxane, or a mixture thereof.

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[0081] 62. The method of item 58, wherein the polymer includes a polymer having a conjugated polymer backbone, a polymer having an aromatic polymer backbone, or a mixture thereof.

[0082] 63. The method of item 58, wherein the polymer comprises a conductive polymer.

[0083] 64. The method of item 58, wherein the composite material has at least about 25% by weight inorganic particles.

[0084] Brief Description of the Drawings

[0085] FIG. 1 is a schematic diagram of a specific embodiment of a polymer/inorganic particle composite material.

[0086] FIG. 2 is a schematic diagram of another specific embodiment of a polymer/inorganic particle composite material with a low-degree cross-linking network.

[0087] FIG. 3 is a schematic diagram depicting the bonding of inorganic particles with various linking agents to form a star bond in a composite material.

[0088] FIG. 4 is a schematic diagram of yet another specific embodiment of a polymer/inorganic particle composite with a high degree of crosslinkability.

[0089] FIG. 5 is a schematic diagram of a specific embodiment of a polymer/inorganic particle composite material in which particles are bonded to polymer chains.

[0090] FIG. 6 is a schematic diagram of a copolymer having characteristics of a partial bonding embodiment of a polymer/inorganic particle composite material.

[0091] FIG. 7 is a schematic diagram of a specific embodiment of a polymer/inorganic particle composite material with cross-linked bonding particles.

[0092] FIG. 8 is a schematic diagram depicting an inorganic particle that forms a bond with one of the blocks of the block copolymer via a linking compound.

[0093] FIG. 9 is a schematic diagram depicting a composite material formed using two kinds of inorganic particles bonded to different blocks of a diblock copolymer.

[0094] FIG. 10 is a schematic diagram of an integrated device (at least a portion of which includes a polymer/inorganic particle composite).

[0095] FIG. 11 is a schematic diagram of a coupling (which includes a polymer/inorganic particle composite).

[0096] FIG. 12 is a top plan view of a field effect transistor.

[0097] FIG. 13 is a side plan view of the field effect transistor of FIG. 12.

[0098] FIG. 14 is a perspective view of a laser pyrolysis apparatus used to manufacture titanium oxide.

[0099] FIG. 15 is a cross-sectional side view of the laser pyrolysis apparatus of FIG. 14.

[0100] FIG. 16 is a cross-sectional view of the laser pyrolysis apparatus of FIG. 14 taken along line 16-16 of FIG. 14.

[0101] FIG. 17 shows the x-ray diffraction patterns of three different TiO2 powder samples.

[0102] FIG. 18 is a graph of the relative grade of the formed dispersion as a function of the dielectric constant of the solvent.

[0103] FIG. 19 is an absorption spectrum expressed in arbitrary units as Ti0₂-l ethanol 0.003% by weight dispersion as a function of wavelength.

[0104] FIG. 20 is an absorption spectrum expressed in arbitrary units as Ti0₂-2 a graph of the wavelength of a 0.003% by weight ethanol dispersion as a function of wavelength.

[0105] FIG. 21 is an absorption spectrum expressed in arbitrary units as Ti0₂-3 as a function of the wavelength of a 0.003% by weight dispersion of ethanol.

[0106] FIG. 22 is a graph of the absorption spectrum expressed in arbitrary units as a function of the wavelength of a 0.003 wt% ethanol dispersion of a commercial brand of TiO2.

[0107] FIG. 23 is an absorption spectrum expressed in arbitrary units as a function of the wavelength of the 0.003% by weight ethanol dispersion of the second commercial brand TiO2.

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[0108] FIG. 24 is a Fourier transform-infrared absorption spectrum of polyacrylic acid alone and two poly(acrylic acid) titanium oxide composite materials.

[0109] FIG. 25 is a graph of Fourier transform-infrared absorption spectra of poly(acrylic acid) titanium monoxide composites processed at three different temperatures.

[0110] FIG. 26 shows the poly(acrylic acid)-TiO formed using 10% by weight loading of silylated particles₂A scanning electron micrograph of the composite material magnified by a magnification.

[0111] FIG. 27 is a scanning electron micrograph of the composite sample of FIG. 26 at a higher magnification.

[0112] FIG. 28 is a poly(acrylic acid)-TiO formed using untreated particles with a loading amount of 10% by weight₂A scanning electron micrograph of the composite material magnified by a magnification.

[0113] FIG. 29 is a scanning electron micrograph of the composite sample of FIG. 28 at a higher magnification.

[0114] FIG. 30 shows the poly(acrylic acid)-TiO formed using 10% by weight loading of silylated particles₂A scanning electron micrograph of the composite material magnified by a magnification.

[0115] FIG. 31 is a scanning electron micrograph of the composite sample of FIG. 30 at a higher magnification.

[0116] FIG. 32 is a poly(acrylic acid)-TiO formed using untreated particles with a loading amount of 10% by weight₂A scanning electron micrograph of the composite material magnified by a magnification.

[0117] Figure 33 is a scanning electron micrograph of the composite sample of Figure 32 at a higher magnification.

[0118] FIG. 34 shows the poly(acrylic acid)-TiO formed using 10% by weight loading of silylated particles₂A scanning electron micrograph of the composite material magnified by a magnification.

[0119] FIG. 35 is a scanning electron micrograph of the composite sample of FIG. 34 at a higher magnification.

[0120] FIG. 36 shows the poly(acrylic acid)-TiO formed using untreated particles with a loading of 10% by weight₂A scanning electron micrograph of the composite material magnified by a magnification.

[0121] FIG. 37 is a scanning electron micrograph of the composite sample of FIG. 36 at a higher magnification.

[0122] FIG. 38 is a scanning electron micrograph of a poly(acrylic acid) (250,000 MW) TiO2 composite formed by using 50% by weight filling of silylated particles.

[0123] FIG. 39 is a scanning electron micrograph of the composite sample of FIG. 38 at a higher magnification.

[0124] FIG. 40 is a magnified scanning electron micrograph of a poly(acrylic acid) (250,000MW) Ti02 composite formed using untreated particles with a filling amount of 50% by weight.

[0125] FIG. 41 is a scanning electron micrograph of the composite sample of FIG. 40 at a higher magnification.

[0126] Figure 42 shows two poly(acrylic acid) samples and two poly(acrylic acid)-TiO₂Differential scanning calorimetry of composite materials.

[0127] FIG. 43 is a scanning electron micrograph of a polyamide polymer film obtained from the polymerization of 6-amino-hexanoic acid at a magnification of one magnification.

[0128] FIG. 44 is a scanning electron micrograph of the film of FIG. 43 at a higher magnification.

[0129] FIG. 45 is a scanning electron micrograph magnified by a magnification of a polyamide-TiO2 composite formed using untreated particles with a filling amount of 50% by weight.

[0130] FIG. 46 is a scanning electron micrograph of the composite of FIG. 45 at a higher magnification.

[0131] FIG. 47 is a magnified scanning electron micrograph of a polyamide-TiO 2 composite formed using 50% by weight of the silylated particles.

[0132] FIG. 48 is a scanning electron micrograph of the composite material of FIG. 47 at a higher magnification.

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[0133] FIG. 49 is a Fourier transform-infrared spectrogram of a composite material formed by two kinds of adipic acid and TiO2 polymer.

[0134] Detailed description of specific embodiments

[0135] Generally, the linking compound can be chemically bonded to the inorganic nanoparticle and monomer/polymer unit to form a composite or mixed material, but in some embodiments, the polymer can be directly bonded to the inorganic particle. Pick up. By using the linking compound, a stable uniform polymer-inorganic particle composite material with highly dispersed inorganic particles can be formed. Specifically, high particle loading can be achieved without agglomeration of particles, but the condition is that the particles must be functionalized with groups that are not easily bonded to themselves, and the self-bonding of these groups can lead to the formation of hard attachments. Polymer. The composite material can represent the synergy of the combined components. The composition has advantages in terms of structure, electronic or optical properties.

[0136] The composite material can be used to form a layer on a substrate to form various useful devices (especially optical devices and photonic crystals). Similarly, for example, the composite material can be positioned into a specific device through self-assembly via a suitable positioning route. Alternatively, the composite material can be formed into a free-standing structure, for example, a fiber.

[0137] Therefore, the composite material includes a monomer/polymer component, inorganic particles, and a connecting compound that can bridge the inorganic particles and the monomer/polymer. With regard to the monomer unit connected to the linking compound, as the composite material is formed, a polymer can be formed. For the convenience of explanation, the monomer/polymer unit connected to the linker and assembled into the composite material is generally called a polymer, although it is known that in some cases, the unit may be a monomer or a polymer, for example, Dimer, trimer or larger polymer structure.

[0138] Some polymers suitable for incorporation into the composite material include organic polymers and inorganic polymers, such as polysiloxanes. If the polymer is formed before reacting with the functionalized inorganic particles, the molecular weight of the polymer can be selected to change the properties of the composite material formed. The polymer containing a suitable functional group is selected or synthesized so as to covalently bond with the functional group of the linking compound.

[0139] The linking compound has 2 or more functional groups, one of which is suitable for chemical bonding with the inorganic particles. Chemical bonding is considered to broadly include bonds with partial covalent properties, which may or may not include polar bonding, and may have the properties of ligand-metal bonding and various degrees of ionic bonding. As described further below, the functional group can be selected according to the composition of the inorganic particles. Another functional group is suitable for covalent bonding with the polymer. Covalent bonding broadly refers to having. Bonds, other non-localized covalent bonds and/or other types of covalent bonding, and may be polarized bonds with or without ionic bonding components and the like. Conveniently used linking agents include functionalized organic molecules.

[0140] In certain embodiments, the polymer may be combined with the inorganic particles to form a polymer network. This can be accomplished by reacting the functional groups of the linking compound with the end groups of the polymer molecule. Alternatively, the inorganic particles may be present during the polymerization process, so that the functionalized inorganic particles may be directly incorporated into the polymer structure when it is formed. In other embodiments, the inorganic particles are grafted onto the polymer by reacting the linker functional group with the functional group on the side group of the polymer. In any of these embodiments, if there are enough linker molecules (that is, enough to overcome the energy barrier and form at least 2 or more bonds that can connect the polymer), the surface-modified/functionalized inorganic The particles can crosslink the polymer. Generally, inorganic particles have many linking agents associated with the particles. Therefore, in fact, the cross-linking effect depends on the polymer-particle arrangement, and the statistical interaction of the two cross-linking groups combined with molecular dynamics and chemical dynamics.

[0141] A series of filling amounts of the inorganic particles can be mixed into the composite material. It can be made into a composite material with high uniformity and low particle filling. In addition, a high filling amount of inorganic particles up to about 50% by weight or more with well-dispersed particles can be obtained. In addition, the amount of the linking compound bonded to the inorganic particles can be adjusted to change the amount obtained by using the polymer.

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The degree of crosslinking obtained.

[0142] The inorganic particles generally contain metal or metalloid elements in their elemental or compound form. Specifically, the inorganic particles may contain, for example, elemental metals or elemental metals (ie non-ionized elements), metal/metalloid oxides, metal/metalloid nitrides, metal/metalloid carbides, metal/metalloids Metalloid sulfides or combinations thereof. Metalloids are elements with chemical properties between metals and non-metals or including metals and non-metals. Metalloid elements include silicon, boron, stele, baht, and yards. Preferably the average diameter of the particles is less than about 500 nanometers (nm). For example, suitable nanoparticle can be formed by flame synthesis method, combustion method, or sol-gel method. A preferred method of synthesizing the particles includes laser pyrolysis, where light from a densely focused source can drive the reaction to form the particles. Laser pyrolysis can be used to form particles with high uniformity in composition, crystallinity and size.

[0143] In order to form the desired composite material, the inorganic particles can be chemically bonded to one or more linking agent molecules to change their surface properties. The ratio of the linking agent component to the inorganic particles is preferably at least one linking agent molecule per inorganic particle. The linker molecule can change the surface properties of the inorganic particles, that is, functionalize the inorganic particles. Although the linker molecule can be bonded to the inorganic particle, it is not necessarily bonded to the inorganic particle before it is bonded to the polymer. It can be bonded to the polymer first and then to the particle. Or, it can be bonded to these two substances at the same time.

[0144] An important procedure in the preferred method for synthesizing the composite material involves dispersing the inorganic particles in a liquid. The solvent, pH, ionic strength and other additives can be selected to improve the dispersibility of the particles. The better dispersibility of the particles and the stability of the dispersion help to reduce the agglomeration of the particles in the formed composite material.

[0145] During or after forming the particle dispersion, the dispersion may interact with the linker molecule and/or the polymer. Generally, the linking agent is soluble in the liquid used to form the inorganic particle dispersion and/or the polymer dispersion, so when bonding from the solution, the linking agent can be uniformly dissolved. The conditions used for the combined particle dispersion and polymer dispersion/solution should be suitable for forming the bond between the linking agent, the inorganic particles and the polymer. The order of adding the linking agent to the inorganic particles and the polymer can be selected to obtain the desired processing efficiency. Once sufficient time has passed to complete the bonding between the components of the composite material, further processing steps of the composite material can be carried out.

[0146] Once the polymer-inorganic particle composite is formed, it can be transferred to another solvent or removed from the original solvent. The composite material can be molded, extruded, cast, or processed using other polymer processing techniques to form various material shapes. In addition, a slurry mainly containing a solvent may be used to coat the composite material by a spin coating method (or the like) to form a coating of the composite material. After the coating is formed, any solvent can be removed. Standard masking techniques can be used to form the coating. In addition, as described further below, the properties of each component of the composite material can be used to help form a structure on the substrate through self-assembly technology.

[0147] Since a variety of inorganic particles and polymers can be incorporated into the composite material described in the text, the composite material is suitable for a variety of applications. In particular, the composite material can be used in the fields of optics and electronics. For example, if the inorganic particles have a high refractive index, various optical devices or optical coatings can be formed with a wide range and controllable refractive index value. For example, the composite material can be used to form a high refractive index coating on an optical fiber. It is best to use high refractive index materials to control light propagation. The filling amount of particles can be adjusted to control the refractive index of the composite material.

[0148] Other composite materials of inorganic particles and polymers have been proposed for some specific applications. For example, Dallmann et al., U.S. Patent No. 5,698,309 entitled Molded Bodies Made of Polyester Containing Covalent Bonded Oxide Particles, cited herein, discloses a molded article containing polyester polymer and oxide particles. Similarly, Kinkel et al., cited here, named Surface-Modified Oxide Particles And Their Use As Fillers An Modifying Agents In Polymer Materials in the United States Patent

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No. 5,494,949 discloses polyester monoxide particle composite materials. In addition, US Patent No. 5,965,299 (which is incorporated herein by reference) issued to Khan et al., entitled Composite Electrolyte Containing Surface Modified Fumed Secica, discloses a solid lithium electrolyte containing a composite material of vinyl polymer and silicon oxide particles. The types of the polymer, inorganic particles, composite material structure and/or the type of bonding in these patents are different from the corresponding composite materials and components described in various specific embodiments herein. In addition, different applications and processing methods for polymer/inorganic particle composites have been discovered.

[0149] Polymer and Inorganic Particle Composite Material

[0150] The polymer-inorganic particle composite material described herein includes inorganic particles bonded to the polymer, and preferably the inorganic particles are bonded to the polymer via a connecting compound. The linking compound is a multifunctional compound that can chemically bond with the inorganic particle and the polymer, for example, a bifunctional compound. The chemical bond between the polymer and the linking agent is usually a covalent bond. The chemical bond between the linking agent and the inorganic surface of the particle usually includes a chemical bond between a functional group and the metal atom and possibly other atoms in the inorganic component.

[0151] After the linking agent is bonded to the polymer and the inorganic particles, a bond is formed, which includes a functional group formed to link the linking compound to the polymer, and to make the linking compound and the inorganic Another functional group formed by particle linkage. The formed or generated functional group is the reaction product of the reaction involving the initial linker functional group. Therefore, various functional groups formed in the bond between the polymer and the inorganic particles can be used to confirm the linking agent originally present in the formed composite material. According to the characteristics of the functional group formed, the characteristics of the functional group of the starting linking compound may or may not be uniquely confirmed in the final composite material. For example, if multiple linker molecules are included, if the linker contains more than two functional groups, or if the polymer side chain initially contains more than one functional group, more than two functional groups may be found on the bond.

[0152] Via the linking compound, the inorganic particles can be bonded within the polymer structure, or the particles can be grafted onto polymer side groups. In most embodiments, the bonded inorganic particles can crosslink the polymer. Specifically, most specific embodiments involve star crosslinking of a single inorganic particle with several polymer groups. The structure of the composite material can usually be controlled by the following factors: the density of the linking agent, the length of the linking agent, the chemical activity of the coupling reaction, the density of the active groups on the polymer and the filling amount of the particles, and the molecular weight range of the polymer (also That is, monomer/polymer unit). In other embodiments, the polymer has a functional group that can be directly bonded to the inorganic particle at a terminal position or a side group. In these other embodiments, the polymer includes functional groups that can be comparable to the functional groups of a suitable linker bonded to the inorganic particles.

[0153] The composite material preferably has stable integral inorganic particles that can be sufficiently dispersed throughout the structure of the composite material. Using this method, a high filling amount of inorganic particles can be obtained, and the particles in the composite material will not have obvious agglomeration. A stable composite material can be prepared using inorganic particles with a filling amount greater than about 50% by weight (and can be greater than about 80% by weight). Those skilled in the art understand that the particle filling amount below these specific values is covered by the scope of the disclosure herein, and it is a suitable cut-off value for some filling amounts. For some applications, low filling levels (for example, 1% or 2% or less) are preferred.

[0154] In order to form a high refractive index material, a high particle filling amount is usually used. The refractive index volume ratio of the inorganic particles and the polymer shows that the refractive index of the composite material is approximately a linear combination. Compared with larger inorganic particles, the advantages of using the nanoparticle are that the optical material has higher transparency and the light scattering phenomenon is reduced, especially the infrared part of the electromagnetic spectrum (which includes the wavelength of about 0.8 microns to about 5.0 microns) can be effectively reduced. ) Of the scattering phenomenon.

[0155] Various structures can be formed according to the basic idea of forming the chemically bonded polymer/inorganic particle composite material. So

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The resulting structure usually depends on the relative amounts of the polymer/monomer, linking agent, and inorganic particles, as well as the synthesis method itself. Linking agents can also be considered coupling agents or crosslinking agents. The first composite material structure is shown in Figure 1. The composite material 100 includes inorganic particles 102, polymer molecules 104, and a linking agent 106. In this specific embodiment, each molecule of the inorganic particles has about 1 linking bond to the end of the polymer molecule. This specific embodiment only briefly describes a few principles, but in fact, usually many linking agents can be bonded to each particle to obtain the desired degree of bonding between the polymer and each particle. The chemical/covalent bonds 108 between these parts are indicated by dots.

[0156] In the structure shown in Figure 1, each inorganic particle can be bonded to about one polymer chain, but usually at least a small part of the inorganic particles are not bonded to the polymer chain, or are bonded to more than one polymer chain. . Even if there is an average of one linking agent per inorganic particle, the structure of FIG. 1 may not be formed. According to the conditions used when the linking agent is combined with the inorganic particles, some inorganic particles can be bonded to two or more linking agents, while other inorganic particles may not be bonded to any linking agent.

[0157] In addition, the relative amount of the polymer and the surface-modified particles will affect whether the polymer molecule is bonded to the inorganic molecule and the linking agent at both ends or only at a single end position. For example, if the polymer is present at a significantly higher equivalent/molar concentration, most polymer molecules can have at most one bonded inorganic particle. However, on the other hand, the mixing amount and other processing parameters can also affect the final structure.

[0158] Generally, many cross-linking molecules can be bonded to each inorganic particle. Since an appropriate amount of the linking agent is bonded to the polymer, the inorganic particles with the bonded linking agent can crosslink the polymer. For example, the structure of a cross-linked inorganic particle is shown in FIG. 2. In this specific embodiment, the composite material 110 includes a plurality of inorganic particles 102 bonded to a plurality of linking agents 106. The inorganic particles modified by the linking agent then crosslink the polymer molecules 104. The figure is represented by a set of representative component symbols. The ellipsis is used to indicate a continuously cross-linked structure.

[0159] The main difference between the structure of FIG. 1 and the structure of FIG. 2 is the relative amount of connections. The structure of Fig. 1 has about one linking agent molecule per inorganic particle, and the structure of Fig. 2 has more than one linking agent per inorganic particle. As mentioned above, if many particles can be bonded to more than one linking agent molecule, while other particles cannot be bonded to the linking agent, the surface modification of the particle is performed, even if there is approximately one linking agent per inorganic particle, The surface-modified inorganic particles can also crosslink the polymer. The detailed structure of the cross-linked polymer (as shown in Figure 2) depends on the relative amount of the linking agent, inorganic particles, and polymer molecules, as well as the size of the linking agent, the chemical reactivity of the linking agent and the processing conditions . The linking agent can have more than two functional groups, so the linking agent can also crosslink the composite material.

[0160] In a preferred embodiment, the linking agent can be used to form at least most of the monolayer on the particle surface. In particular, it is preferred that at least about 20% of the monolayer is applied to the particles, and usually at least about 40% of the monolayer is applied. The monolayer is calculated based on the measured surface area of the particle and the molecular radius of the linking agent estimated on the basis of the acceptable value of the atomic radius. Due to the high linking agent content, it can be assumed that the linking agent can form a highly crosslinkable structure with the polymer. In each inorganic particle, a star-shaped crosslinked structure can be formed. It is shown graphically in FIG. 3, where the inorganic particles 102 are bonded to a number of linking agents 106, and the linking agent 106 is then bonded to the polymer 104. A highly cross-linkable structure can be formed around the star-shaped bond of the inorganic particles. It is expected that these structures are also related to low particle concentration or polymer growth from the particle surface.

[0161] Another composite material structure 112 is shown in FIG. 4, wherein the polymerization reaction is carried out in the presence of the surface modified inorganic particles. The particles become an indispensable part of the polymer structure. A variety of different monomer units can be used to form copolymers. A properly selected functional group and/or polymerization conditions that can form a sequential polymerization reaction are used to form a block copolymer. Block copolymers are described further below. In the specific embodiment of FIG. 4, the relative amount of the monomer 114 relative to the inorganic particles 102 and the linking agent 106 determines a clear structure. As shown in Figure 4, the monomer 114 and other monomers

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114 or the linking agent 106 is bonded. In other embodiments, the monomer may include a functional group that is only bonded to the linker molecule and not to other monomers. In this other structure, the surface-modified inorganic particles are indispensable elements for forming the polymer, and the inorganic particles and the linking agent can be used as repeating units in the polymer.

[0162] The degree of crosslinking in the composite material 112 of FIG. 4 depends on the relative amount of the linking agent compared to the inorganic particles and monomers. In addition, the monomer may have 3 or more covalent bonds to form crosslinks between itself. Therefore, various structures can be formed. In Fig. 4, only representative labeled samples are clearly shown, and ellipsis is used to further indicate the structure.

[0163] A specific embodiment of the grafted inorganic particle composite material is shown in FIG. 5. The composite material 140 includes a polymer 142 having a monomer 144 containing functional pendant groups 146. The side group 146 is covalently bonded to the linking agent 106, wherein the linking agent 106 is chemically bonded to the inorganic particles 102. Of course, if an insufficient amount of surface-modified inorganic particles is used, or if the frequency of the side groups is too high (in the case of polyacrylic acid), the side groups 146 may not be connected to the inorganic particles 102. The linking agent 106 is bonded.

[0164] Another specific implementation is shown in FIG. 6. In the specific embodiment of FIG. 6, the composite material 160 includes a copolymer 162 containing a monomer 164 with functional side groups 166 and a monomer 168 without functional side groups. The degree of grafting of the inorganic particles can be controlled by the relative amount of monomers with functional side groups relative to the total number of monomers.

[0165] If the amount of the linking agent molecule increases, the grafted inorganic particles can also form crosslinks between polymer chains. Referring to FIG. 7, the composite material 180 includes a polymer molecule 182 having a monomer 184 with functional side groups 186 and a monomer 188 without functional side groups. The inorganic particles 102 with the linking agent 106 can be cross-linked between two functionalized side groups. The degree of crosslinking depends on the relative amounts of all the ingredients.

[0166] In all of the structures in Figures 1-7, block copolymers may be formed. For example, the polymer chain bonded to the linking agent may itself be a block copolymer. Therefore, the structure formed is a block copolymer linked to inorganic particles. In one form, the inorganic particles that have been bonded to the linking agent can crosslink the block copolymer in the manner of a star-shaped bond in FIG. 3. Such a block copolymer is shown in Figure 8. The inorganic particles 200 are bonded to the linking agent 202. The linking agent 202 is bonded to the block copolymer 204 having blocks 206 and 208.

[0167] As shown in FIG. 8, the inorganic particles may be bonded to the polymer by the side groups of the copolymer to crosslink the composite material. Generally, the inorganic particles may be bonded to the side groups of only one block or two blocks of the polymer. As shown in FIG. 8, the inorganic polymer is only grafted with the block 206 of the copolymer 204.

[0168] In other other embodiments, each block may be bonded to different types of modified inorganic particles. For example, an inorganic particle can be bonded to a linking agent molecule, and a second inorganic particle is bonded to a second linking agent. A linking agent has a bond that can be bonded to a block of the block copolymer. Suitable functional groups, and the second linking agent has suitable functional groups that can be bonded to another block of the block copolymer.

[0169] Such a copolymer is shown in Figure 9. The composite material includes a first type of inorganic particles 220 and a second type of inorganic particles 222. The difference between different types of particles lies in their composition, crystalline structure and/or physical properties. The inorganic particles 220 are bonded to the first linking agent 224, and the inorganic particles 222 are bonded to the second linking agent 226. The linking agent 224 is bonded to the first block 228 of the block copolymer 230, and the linking agent 226 is bonded to the second block 232 of the block copolymer 230.

[0170] If the chemical composition of different blocks is selected to have different chemical properties in terms of charge, polarity, hydrophobicity, etc., there will be a tendency to segregate in the solution of the block. This segregation phenomenon is a self-organizing type. Self-organization can be used for self-assembly.

[0171] The difference in properties between various embodiments depends on the details of the chemical part, the relative amounts of the components, and the structure of the composite material. A representative embodiment of the composite material has been described. Obviously, combining composite materials with various characteristics

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Other variations in the structure can be obtained by combining and/or changing the characteristics of the above-mentioned various composite material structures. The exact structure of the composite material depends on the nature of the polymer and linking agent, the relative amounts of the components, and the processing conditions.

[0172] The selection of the inorganic particles can produce the desired properties of the composite material formed. For example, the inorganic particles can be selected according to the following conditions: their optical properties, conductivity, electrical/magnetic properties, thermal properties (for example, thermal expansion), luminescence, or catalytic activity. Suitable inorganic particles include, for example, metal/metalloid particles, metal/metalloid oxides, metal/metalloid nitrides, metal/metalloid carbides, metal/metalloid sulfides, metal/metalloid phosphates and their mixture. The preferred properties and the method of synthesizing the preferred inorganic particles are detailed in the following paragraphs.

[0173] Suitable polymers include organic polymers, silicon-based polymers, and other inorganic polymers. Many different polymer types are suitable as long as they have end groups and/or preferably side groups that can be bonded to the linking agent. Suitable organic polymers include, for example, polyamide (nylon), polyimide, polycarbonate, polyurethane, polyacrylate, polyacrylic acid, polyacrylate, polyacrylamide, polyvinyl alcohol, Polyvinyl chloride, heterocyclic polymers, polyester and modified polyolefin blanks. The composite material formed by using nylon polymer (ie, polyamide) and inorganic nanoparticles can be called NanonylonTM_oSuitable polymers include conjugated polymers in the polymer backbone, for example, polyethylene; and aromatic polymers in the polymer backbone, for example, poly(p-phenylene), poly (Phenylene vinylene), polyaniline, polythiophene, poly(phenylthiophene), polypyrrole and its copolymers and derivatives. Part of the polymer may be bonded to the linking agent at the functional side group. The polymer can essentially contain desired functional groups, can be chemically modified to introduce desired functional groups, or copolymerized with monomer units to introduce some desired functional groups. Conductive polymers are especially useful in certain applications. Once doped with electron acceptors (for example, halogens) or electron donors (for example, alkali metals), polyethylene can become an electrical conductor. In many embodiments, although one of the aforementioned polymers is present in an amount of at least about 50% by weight of the polymer/monomer component (optionally at least about 75%, and optionally at least about 90%) It is also possible to use mixtures of polymers. Similarly, some composite materials only contain a single polymer/monomer component that can be bonded within the composite material. In the cross-linked structure, in addition to the blank chain that is not considered a polymer (unless it has repetitive side groups or has at least about 50 carbon-carbon bonds in the chain), there can be 3 or more along the chain On the repeating unit to identify a polymer.

[0174] Preferred silicon-based polymers include polysilane and polysiloxane (silicone) polymers, for example, poly(dimethylsiloxane) (PDMS). Polysiloxanes are particularly suitable for forming composite materials with grafted inorganic particles. In order to form these grafted composite materials, the polysiloxane can be modified by amino acids and/or by acid groups. Polysiloxanes are preferred polymers because of their transparency to visible light and ultraviolet light, high thermal stability, resistance to oxidative degradation, and their hydrophobicity. Other inorganic polymers include, for example, phosphorescent polymer (phosphonitrite polymer).

[0175] Polyamides are preferred because unreacted acid groups or amine groups can be used to covalently bond the polymer and the linking compound. Various polyamides are available and possess the desired mechanical properties, for example, Nylon 6. The importance of polyimide lies in its excellent structural and thermal properties. In particular, some polyimides have high thermal stability. In terms of low temperature processing, some fluorinated polyimides are curable under ultraviolet light. In addition, some polyimides are at least partially transparent to infrared rays. In addition, polyimide may have liquid crystal properties. The polyimide can be directly bonded to various functional groups of the linking agent or via functional side groups.

[0176] Vinyl polymers are attractive because of their low cost and flexibility in choosing the nature of the desired side groups, and many different vinyl polymers are available. Vinyl polymers can be synthesized by free radical initiation. Of particular importance are acrylic polymers because of their transparency and functionalization of side groups. In addition, acrylic polymers can be copolymerized to form block copolymers, which can be used to form organized nanoscale structures.

[0177] The linking agent is a multifunctional molecule having at least one functional group that can be bonded to the inorganic particle, and

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At least one functional group that can be bonded to the polymer. The functional group is preferably located in the linking agent molecule, so there will be no steric interference with the bonding to the inorganic particles and the bonding to the polymer. Therefore, the linking agent can provide bonding capabilities capable of forming composite materials. In a preferred embodiment, the functional group to be bound to the inorganic particles is chemically and functionally different from the functional group bound to the polymer, so the linking agent does not only cross-link the polymer or inorganic particles together. No composite material is formed. The linking agent may contain more than two functional groups, so chemical crosslinks can be formed in the composite material. Moreover, the linking agent should be treated in a way that can reduce (preferably as much as possible) the self-condensation reaction of the linking agent. For poly-alkoxy or poly-chlorosilanes that can be polycondensed to form oligomeric or resin-like linking agents, the above-mentioned treatment method is particularly appropriate.

[0178] The linker framework supporting the functional group is usually an organic compound, but may also contain silyl and/or siloxy moieties. The organic linker framework can comprise any suitable organic moiety, which includes, for example, linear or branched carbon chains, cyclic carbon moieties, saturated carbon moieties, unsaturated carbon moieties, aromatic carbon units, halogenated carbon groups, And its composition. The structure of the linking agent can be selected to obtain the desired properties of the composite material. For example, the size of the linking agent can affect the repeatability and self-organization properties of the composite.

[0179] Suitable functional groups to bind to the polymer depend on the functionality of the polymer. Generally, the functional group of the polymer and the linking agent can be appropriately selected according to the known bonding properties. For example, acid groups can be covalently bonded to thiols, amines (primary and secondary amines), and alcohol groups. As a specific example, nylon may include unreacted acid groups, amine groups, or derivatives thereof, which are suitable types that can be covalently bonded to a linking agent. In addition, in terms of bonding with acrylic polymers, a part of the polymer can be formed from acrylic acid or its derivatives, so the acrylic acid can be bonded with the amine (primary amine and secondary amine), alcohol or thiol of the linking agent . The functional group of the linking agent can selectively bond only particles with a specific composition and/or a polymer with a specific functional group. Other suitable functional groups of the linking agent include, for example, halogen, silyl (-SiR³-_xH_x), isooxoate, oxoate, sulfoate, epoxy, vinylsilyl, silyl hydride, silyl halide, mono-, di- and tri-halogenated organosilanes, phosphonates, organometals Acid radical, vinyl group, allyl group and usually any unsaturated carbon group (-R'-C=C-R''), where R'and R'' are any groups that are bonded within the structure . Selective bonding can be used to form a self-organizing composite structure.

[0180] When the polymer functional group reacts with the linker functional group, the characteristics of the starting functional group can be incorporated into the formation or product functional group in the bonded structure. Extension from the polymer can form a bond. The bond extending from the polymer may include, for example, an organic moiety, a siloxy moiety, a sulfide moiety, a sulfonate moiety, a phosphonate moiety, an amine moiety, a dial moiety, a vat moiety, or a combination thereof. According to the functional group formed, the original functional group characteristics can be displayed or not. The functional group formed can usually be, for example, an ester group, an amide group, an acid group, a disulfide group, a sulfide group, a disulfide group, an alkoxy group, a base group, and a carbamic acid group. An ester group, an amine group, an organosilane group, a hydrogen-containing silane group, a silane group, a vatyl silane, a phosphonate group, a sulfonate group or a combination thereof.

[0181] If a linking compound is used, usually one kind of functional group can be formed, wherein the polymer is bonded to the linking agent, and a second kind of functional group can be formed, wherein the linking agent is bonded to the inorganic particles. In the inorganic particle, the identification of the functional group may depend on whether a specific atom is bound to the particle or the functional group. This is just a question of terminology, and those skilled in the art can identify the structure formed without considering the position of the specific atom in the functional group. For example, the bond between an acid and an inorganic particle can make a group participate in the bonding of the non-metallic/metalloid atom of the particle; however, regardless of the composition of the particle, an oxirane group can usually be present in the formed functional Kine. Finally, chemical bonds can extend to metal/metalloid atoms.

[0182] Suitable functional groups that can be bonded to the inorganic particles depend on the nature of the inorganic particles. Awarded to Kinkel et al., named SURFACE-MODIFIED OXIDE PARTICLES AND THEIR USE AS FILLERS AND

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US Patent No. 5,494,949 of MODIFYING AGENTS IN POLYMER MATERIALS (which is incorporated herein by reference) describes the use of silylating agents to bond metal/metal-like oxide particles. The particle has an alkoxy-modified silane that can be bonded to the particle. For example, preferred linking agents that can be bonded to metal/metal-like oxide particles include R^XR²R³-Si-R⁴, Where P, F, W are alkoxy groups (which can be hydrolyzed and bonded to the particle), and R⁴Is a group suitable for bonding with the polymer. The trichlorosilicate (-SiC13) functional group can react with the vat group on the surface of the metal oxide particle through condensation reaction.

[0183] Generally, thiol groups can be used to bond metal sulfide particles and certain metal particles (eg, gold, silver, cadmium, and zinc). The press base can be bonded with other metal particles (for example, aluminum, titanium, aluminum, hoe and steel). Likewise, amine and hydroxide groups have been expected to bind to metal oxide particles and metal nitride particles and transition metal atoms (eg, iron, drill, rake, and tongs).

[0184] Since the linker functional group has the property of being able to bond with the inorganic particles, the linker functional group bonded to the inorganic particles can also be modified. One or more atoms of the inorganic particles are required to form a chemical bond between the linking agent and the inorganic particles. It is not clear whether one atom in the formed bond comes from the linking compound or the inorganic particle. In any case, the formed or generated functional group can link the linking agent and the inorganic particles. The formed functional group may be, for example, one of the aforementioned functional groups derived from the bonding of the linking agent and the polymer. The functional groups in the inorganic particles are finally bonded with one or more metal/metalloid atoms.

[0185] Inorganic particles

[0186] Generally, any suitable inorganic particles can be used to form the composite material. In a preferred embodiment, the average diameter of the particles does not exceed about 1 micron. In terms of preferred applications, the particle composition is selected to give the composite material the desired properties. In particular, for composite materials with high particle loading, inorganic particles are the main reason for the overall properties of composite materials. Therefore, for example, the optical properties of the polymer and the inorganic particles are important for the formation of optical materials. According to the volume ratio of the refractive index of the inorganic particles and the polymer, it can be predicted that the refractive index of the composite material is approximately a linear combination.

[0187] The particles are preferably formed by laser pyrolysis, and some submicron particles with excellent uniformity can be formed by laser pyrolysis. The processing advantage of small particles is that they can form small structures and smooth surfaces. In addition, the preferred properties of small particles include reducing scattering to lower scattering loss.

[0188] Generally, the average diameter of the primary particles in the collection of particles of interest is less than about 500 nanometers, preferably about 2 nanometers to about 100 nanometers, or about 2 nanometers to about 75 nanometers, or about 2 nanometers. To about 50 nanometers. Those skilled in the art know that other ranges within these specific ranges are also encompassed in the disclosure herein. The particle diameter can be evaluated by a transmission electron microscope. Preferably, the particles include element/nonionic metal/metalloid, metal/metalloid oxide, metal/metalloid nitride, metal/metalloid sulfide, metal/metalloid carbide, or a combination thereof.

[0189] The primary particles may have an approximately spherical coarse appearance, or they may have a rod-like shape, a sheet-like shape, or other non-spherical shapes. In stricter inspection, crystalline particles usually have facets corresponding to the basic crystal lattice. Amorphous particles usually have spherical surfaces. The asymmetry of the particle diameter can be determined based on the average length measured along the major axis of the particle.

[0190] Due to its small size, the primary particles tend to form loose agglomerates due to van der Waals forces and other electromagnetic forces with neighboring particles. As described further below, these agglomerates can be dispersed to a large extent. The particle size of the secondary or agglomerated particles depends on the subsequent processing after the initial formation of the particles and the composition and structure of the particles. In a preferred embodiment, the average diameter of the secondary particles is about 2 nanometers to about 400 nanometers, preferably about 2 nanometers to about 100 nanometers, or about 2 nanometers to about 50 nanometers. Those skilled in the art know that other ranges within these specific ranges are also covered by

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Within the content disclosed in this article.

[0191] Even though the particles can form loose agglomerates, the nanometer level of the primary particles can be clearly seen in the transmission electron micrographs of the particles. The particles generally have a surface area equivalent to the particles expressed in nanometers (as seen in the photomicrograph). Moreover, due to its small size and large surface area per material weight, the particles can exhibit unique properties. As described in U.S. Patent No. 5,952,125 entitled Batteries With Electroactive Nanoparticles issued to Bi et al. (which is incorporated herein by reference), for example, oxide nanoparticle has surprisingly high energy density in lithium batteries.

[0192] The particle size of the primary particles preferably has a high degree of uniformity. As mentioned above, laser pyrolysis can usually make particles with a narrow range of particle diameters. Moreover, thermal processing performed under appropriate mild conditions does not change the narrow range of particle diameters. Since the laser pyrolysis method uses aerosols to deliver the reactants, the particle diameter distribution is particularly sensitive to the reaction conditions. However, if the reaction conditions are properly controlled, an aerosol delivery system can be used to obtain a very narrow distribution of particle diameters. As determined by examination of penetrating electron micrographs, the size distribution of the primary particles is usually such that at least about 95% (and preferably 99%) of the diameter of the primary particles is greater than about 40% of the average diameter, and less than the average About 160% of the diameter. The diameter distribution of the primary particles is preferably such that at least about 95% (and preferably 99%) of the diameter of the primary particles is greater than about 60% of the average diameter and less than about 140% of the average diameter. Those skilled in the art know that other ranges within these ranges are also covered by the content disclosed in this article.

[0193] Moreover, in a preferred embodiment, none of the primary particles has an average diameter that is about 4 times larger than the average diameter (preferably about 3 times larger, more preferably about 2 times larger). In other words, the particle size distribution does not actually have a rear part that can represent a small number of particles with a significantly larger size. It is the result of the small reaction zone of the particle and the corresponding rapid suspension of the reaction. The effective cut-off in the back of the size distribution means that there are less than about 1 particle in 106 having a diameter larger than the specified cut-off value above the average diameter. High particle uniformity can be used in various applications.

[0194] In addition, the nanoparticle preferably has a very high purity. Due to the laser pyrolysis reaction, it is expected that the nanoparticle produced by laser pyrolysis has a higher purity than its reactant, and the crystal formation method can eliminate the contaminants of the particle. Moreover, the crystalline nanoparticle produced by laser pyrolysis has a high degree of crystallinity. Similarly, the crystalline nanoparticle produced by thermal processing also has a high degree of crystallinity. The method of removing impurities on the particle surface is heating, which not only makes it highly crystalline, but also obtains high purity.

[0195] Laser pyrolysis is a method that can effectively prepare a variety of nano-sized particles with a narrow average particle diameter distribution. In particular, laser pyrolysis can be used to prepare various inorganic particles, for example, elemental metal/metalloid particles, metal/metalloid oxide particles, metal/metalloid carbide particles, metal/metalloid nitride particles, and metal/metalloid particles. Metal-like sulfide particles. Alternatively, for example, the flame generating device described in the U.S. Patent No. 5,447,708 entitled Apparatus for Producing Nano scale Ceramic Particles by Helble et al., cited herein, can be used to prepare submicron particles. Also, the submicron particles can be prepared using, for example, the thermal reaction chamber device described in US Patent No. 4,842,832 entitled Ultrafine Spherical Particles of Metal Oxide and a Method for the Production There of Inoue et al., cited herein. In addition, various solution-based methods (eg, sol-gel technology) can be used to prepare sub-micron particles.

[0196] The basic feature of the successful application of laser pyrolysis to the preparation of the desired inorganic nanoparticle is to produce a reactant stream containing a metal/metalloid precursor compound, a radiation absorber, a general and a second reactant. The second reactant can be a source of atoms (eg, oxygen) required for the desired product, or an oxidizing or reducing agent that can promote the formation of the desired product. If the precursor can be decomposed into the desired product under strong light radiation, the second reactant is not required. Similarly, if the metal/metalloid precursor and/or the second

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The reactant can absorb the suitable light radiation, and a separate radiation absorber is not required. The reactant stream can be pyrolyzed by an intense beam (usually a laser beam). When the reactant stream leaves the laser beam, the particles quickly quench.

[0197] A suitable laser pyrolysis device for the preparation of commercial particles by laser pyrolysis has been developed using the reactant inlet tube (which is significantly enlarged in the direction parallel to the path of the laser beam). The high-energy laser pyrolysis device is described in U.S. Patent No. 5,958,348 named Efficient Production of Particles By Chemical Reaction cited herein. The delivery method of the aerosol precursor suitable for the production of particles by laser pyrolysis is described in the US Patent Application Serial No. 09/188,670 entitled "Reactant Delivery Apparatus" by Gardner et al., cited herein.

[0198] Nanoparticles made by laser pyrolysis can be subjected to additional treatments to modify the properties of the particles, such as composition and/or crystallinity. For example, the nanoparticles can be heat-treated in a gas atmosphere before use. Under appropriate mild conditions, heat treatment is effective to modify the characteristics of the particles, and will not damage the ultra-nanoparticles or narrow particle size distribution of the initial particles. For example, the heat treatment of submicron oxidized sail particles is described in Bi et al., U.S. Patent No. 5,989,514 entitled Processing of Vanadium Oxide Particles With Heat cited in this application.

[0199] Several different types of sub-micron or nanometer-sized particles have been prepared by laser pyrolysis (with or without additional heat treatment. As mentioned above, these particles usually have a very narrow particle size distribution.

[0200] In particular, the method of preparing the oxidized sail nanoparticle is described in U.S. Patent No. 6,106,798 entitled Vanadium Oxide Nanoparticles by Bi et al., cited in this application. Similarly, the method for preparing silver oxide nanoparticle is in the U.S. Patent Application No. 09/246,076 of Home et al. named Metal Vanadium Oxide Particles, and now it is the U.S. Patent and U.S. Patent Application No. 09/311,506 of Reitz et al. (Both are quoted here) are described in.

[0201] Moreover, nano-sized manganese oxide particles have been formed by laser pyrolysis. The preparation of these particles is described in Kumar et al., U.S. Patent Application No. 09/188,770 entitled "Metal Oxide Particles (which is incorporated herein by reference). This application describes MnO, MnzOa, Mn₃θ4^Μη₅The production method of θ8.

[0202] Moreover, such as Kumar et al., U.S. Patent Application Serial No. 09/188,768 named Composite Metal Oxide Particles, and Kumar et al., 09/334,203 named Reaction Methods for Producing Ternary Particles, and Horne et al., named As described in U.S. Patent No. 6,136,287 of Lithium Manganese Oxides and Batteries (all three patent documents are cited herein), lithium oxide nanoparticles are prepared by laser pyrolysis with or without subsequent heating treatment.

[0203] The method for preparing the silicon oxide nanoparticle is described in the U.S. Patent Application Serial No. 09/085,514 entitled "Silicon Oxide Particles" by Kumar et al. cited in this application. The patent application describes the amorphous SiO2 Preparation method. The method of synthesizing silicon carbide into silicon nitride by laser pyrolysis is described in the name of Reit ζ et al. "Particle Dispersions" cited in this application in the U.S. Patent Application Serial No. 09/433,202 filed on November 5, 1999. description.

[0204] The preparation method of the titanium oxide nanoparticle is described in Bi et al., U.S. Patent Application Serial No. 09/123,255 entitled Metal (Sil icon) Oxide/Carbon Composites cited in this application. In particular, the application describes the preparation method of the anatase and rutile TiO2. The preparation method of the alumina nanoparticle is described in the U.S. Patent Application Serial No. 09/136,483 named Aluminum Oxide Particles by Kumar et al. cited in this application. In particular, this application discloses the method of making Y-A12O3. Suitable liquid aluminum precursors with sufficient vapor pressure using gaseous transfer include, for example, S-butadiene aluminum oxide (Al (OC Tian 9) 3). Moreover, many suitable solid aluminum parent compounds are available, including

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Including, for example, aluminum chloride (A1C13), ethoxylate (A1(OC2H5)3), and aluminum isopropoxide (A1[OCH(CH₃)₂]3)o

[0205] In addition, the laser pyrolysis method described in the U.S. Patent Application Serial No. 09/042,227 named Tin Oxide Particles by Kumar et al. cited in this application has been able to prepare tin oxide nanoparticles. The preparation of zinc oxide is described in US Patent Application Serial No. 09/266,202 entitled "Zinc Oxide Particles" by Reitz et al. cited in this application. In particular, the preparation of ZnO nanoparticles is described.

[0206] The preparation of iron and iron carbide is cited in this application by Bi et al.'s publication "J. Mater" entitled "Nanocrystalline a-Fe, FesC and Fe?C3 produced by CO2 laser pyrolysis" Re s. Vo 1.8, No. 7, 1666-1674 (July 1993). The preparation method of the iron oxide nanoparticles is cited in the U.S. Patent No. 6,080,337 by Kambe et al., named Iron Oxide Particles. The method for preparing the silver metal nanoparticle is described in the U.S. Patent Application Serial No. 09/311,506 of Reitz et al., named Metal Vanadium Oxide Particles cited in this application.

[0207] The method for preparing iron sulfide (Feι-xS) microparticles by laser pyrolysis is in the Material Research Society Symposium Proceedings of Bi et al. cited in this application, volume 286, pages 161-166 (1993) There is a description. The matrix required for the laser pyrolysis method of iron sulfide is five dial-based iron (Fe(C0)5) and hydrogen sulfide (H₂S)_o

[0208] Laser pyrolysis can also be used to make oxidized lungs. Suitable matrices required for aerosol delivery include, for example, nitrate lung (Ce(NO3)3), chlorinated lung (CeC13) and oxalate lung (Ce₂(C₂04)3)_oSimilarly, laser pyrolysis can be used to prepare zirconium oxide. Suitable aluminum precursors required for aerosol delivery include, for example, aluminum oxychloride (ZrOCL·) and aluminum oxynitrate (Zr0(N03)2).

[0209] In accordance with the method of preparing the silver oxide sail nanoparticle described in the U.S. Patent Application Serial No. 09/311,506 by Reitz et al., cited in this application under the name of Metal Vanadium Oxide Particles, laser pyrolysis Aluminum silicate and aluminum titanate ternary nanoparticles can be prepared. In terms of vapor transmission, suitable precursors for preparing aluminum silicate include aluminum chloride (A1C13) and silicon tetrachloride (SiCl).₄), and in terms of aerosol delivery, suitable precursors are tetra(N-butoxy)silane and aluminum isopropoxide (A1(OCH(CH3)2)3). Similarly, in terms of aerosol delivery, suitable precursors for the preparation of aluminum titanate include sulfuric acid mixtures of aluminum nitrate (A1(NO3)3) and titanium dichloride (Ti02), or aluminum isopropoxide and titanium isopropoxide. (Ti(0CH(CH₃) A mixture of 2) 4).

[0210] Particle Dispersion

[0211] In order to form the composite material, the inorganic particles are usually dispersed in a liquid, and the polymer/monomer components and linking agent are combined. The formation of the particle dispersion is usually a special step of the method. It is preferable to disperse the collection of nano particles sufficiently so as to be uniformly introduced into the polymer composite material. The liquid phase particle dispersion can provide a source of small secondary particles capable of forming the desired composite structure.

[0212] The required amount of the liquid dispersion of inorganic particles generally depends on the particle concentration, the composition of the dispersion, and the method of forming the dispersion. Specifically, the degree of dispersion actually depends on the interaction between the particles, the interaction between the particles and the liquid, and the surface chemistry of the particles. It is related to both bad and energy. The degree of dispersion and the stability of the dispersion are important characteristics for preparing a uniform composite material, and the uniform composite material will not be affected by obvious agglomerated particles.

[0213] Generally, the liquid dispersion refers to a dispersion in which the concentration of particles does not exceed about 80% by weight. As far as the method of forming the particle dispersion is concerned, the specific particle concentration depends on the selected application. In the case where the concentration exceeds about 50% by weight, various factors are important for the formation and properties of the viscous blend of the more dilute particle dispersion parameter. The concentration of the particles can affect the viscosity and can affect the efficiency of the dispersion process. In particular, a high particle concentration will increase the viscosity and make it difficult to disperse the particles to a small secondary particle size, but the application of shear helps the particle dispersion.

[0214] The composition of the dispersion depends on the composition of the dispersant and the nanoparticle. Suitable dispersants include, for example, water,

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Organic solvents (for example, alcohols and greens), and combinations thereof. The choice of the preferred solvent generally depends on the nature of the nanoparticle. Therefore, the dispersant and nanoparticle that are suitable for forming fully dispersed particles should be selected. Although the pH depends on the crystal structure and surface structure, for example, Y soil particles are usually fully dispersed at an acidic pH of about 3-4, and silica particles are usually fully dispersed at an alkaline pH of 9-11. Titanium oxide particles are usually fully dispersed when the pH is close to 7. Generally, it is possible to preferably disperse nano-particles with very little surface charge in a low-polarity solvent. Therefore, the hydrophobic particles can be dispersed in a non-aqueous solvent or an aqueous solution with a low-polarity co-solvent, and the hydrophilic particles can be dispersed in an aqueous solvent.

[0215] Since many polymers are soluble in organic solvents, many embodiments include the formation of non-aqueous dispersions. In organic solvents, it has been found that the properties of the dispersion depend on the dielectric constant of the solvent. As far as TiO2 is concerned, it is possible to form a good dispersion with an intermediate value of the solvent dielectric constant/polarity. It is further described in the following embodiments.

[0216] In addition, the water-based dispersant may include additional components, for example, surfactants, buffers, and salts. For specific particles, the properties of the dispersion can be adjusted by adjusting its pH and/or ionic strength. The addition of inert salts (for example, sodium chloride, potassium chloride, or the like) can change the ionic strength. The presence of the linking agent can affect the properties and stability of the dispersion. As far as TiO2 is concerned, it is further described in the following examples.

[0217] pH can generally affect the surface charge of dispersed particles. At the pH value of the isoelectric point, the least surface charge can be obtained. The reduction in surface charge can further form agglomeration. Therefore, according to the subsequent processing steps, the pH is selected to obtain the desired amount of surface charge. However, the pH of the solution can affect the binding to the linking agent.

[0218] The liquid may exert a solvation-type interaction physical/chemical force on the particles, which helps to form a particle dispersion. Solvation-type interactions can be energetic and/or rotten in nature. Additional components (e.g., surfactants) can be added to the liquid to help form a dispersion of the particles. Suitable surfactants include, for example, octylphenol polyoxyethylene (sold as Triton® X), nonylphenol polyoxyethylene (sold as Doxfax® 9N and Triton® N) and dodecyltrimethyl Desertification saddle (C12TAB, CH₃(CH₂)HN(CH₃) SBr).

[0219] The quality of the dispersion generally depends on the method of forming the dispersion. In the dispersion, in addition to the chemical/physical force exerted by the dispersant and other compounds in the dispersion, mechanical force can be used to separate the primary particles, which can be aggregated by van der Waals forces and other short-range electromagnetic forces between adjacent particles Together. In particular, the strength and duration of the mechanical force applied to the dispersion can greatly affect the properties of the dispersion. Mechanical force can be applied to the powder and then dispersed in a solvent. Alternatively, after combining one powder or several powders with one liquid or several liquids, mechanical force (for example, shear stress) can be applied to mix, agitate, jet impact and/or ultrasonic treatment.

[0220] The secondary particle size refers to the particle size of the particle agglomerates formed after the powder is dispersed in the liquid. If the agglomeration force between the primary particles is destroyed more, the size of the secondary particles obtained is smaller. If the force between the particles is completely destroyed, at least some secondary particles with the same secondary particle size as the primary particle size can be obtained. The use of surfactants and high shear stress helps to obtain smaller secondary particle sizes.

[0221] The secondary particle size in the liquid dispersion can be determined by established methods (for example, dynamic light scattering). Suitable particle size analyzers include, for example, the Microtrac UPA instrument (from Honeywell) based on dynamic light scattering and the ZetaSizer Series instrument (from Malvern) based on Photon Correlation Spectroscopy. The principle of dynamic light scattering for the determination of particle size in liquids has now been fully established.

[0222] The advantage of the small secondary particle size is that the dispersion can be used to form a composite material with uniform properties. For example, a smaller secondary particle size and a smaller primary particle size can generally help the composite material to form a smoother and/or smaller and more uniform structure. When forming the coating, the composite material formed by the inorganic particle dispersion of the smaller secondary particles can form a thinner and smoother coating. In a preferred embodiment, the average secondary particle diameter is less than about 1000 millimeters

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Micrometer, preferably less than about 500 nanometers, more preferably about 2 nanometers to about 300 nanometers, still more preferably about 2 nanometers to about 200 nanometers, and still more preferably about 2 nanometers to about 100 nanometers. In terms of a specific particle set, of course the primary particle size is the lower limit of the secondary particle size, so the average secondary particle size is preferably about the average primary particle size. For some particle dispersions, the secondary particle size can be close to the primary particle size, which means that the particles are fully dispersed.

[0223] After the dispersion is formed, it can be separated finally, so the particles can be concentrated at the bottom of the container without continuous mechanical stirring or agitation. The particles in the stable dispersion will not separate from the dispersion. Different dispersions have different degrees of stability. The stability of the dispersion depends on the nature of the particles, other compositions in the dispersion, the treatment method used to form the dispersion, and the type of stabilizer. Suitable stabilizers include, for example, surfactants. Although a suitable processing method for forming composite materials can be used to ensure constant mixing and prevent the separation of particle dispersions, the dispersions preferably have appropriate stability. Therefore, when performing subsequent processing steps to form composite materials, use dispersions. There may be no obvious separation.

[0224] Formation of Composite Material

[0225] The linking compound and polymer/monomer components can be added simultaneously or sequentially to the liquid with the particle dispersion. In order to get the desired result, you can choose the order in which the various components are combined. The conditions of use of the liquid are preferably suitable for forming chemical bonds with the linking agent, and can form other chemical bonds with the polymer/monomer components. After forming the composite material, the liquid can be removed or solidified to leave the structure formed from the composite material.

[0226] The polymer/monomer composite material can be formed into a solution/dispersion before being added to the inorganic particle dispersion, or the polymer/monomer can be added in a solid form to the particle dispersion Inside. In a preferred embodiment, the polymer/monomer composition can be dissolved in the liquid used to form the particle dispersion. If the polymer/monomer is not soluble/dispersible in the particle dispersion, you can slowly add the polymer/monomer solution to the particle dispersion or add the particle dispersion to the polymer/monomer solution while mixing to produce reaction. Regardless of whether the polymer/monomer is first dissolved, the separation from the inorganic particle dispersion may depend on the polymer/monomer dissolution kinetics and the desired concentration of the various solutions/dispersions. Likewise, bonding kinetics can affect the sequence and details of the mixing procedure.

[0227] The linking agent can generally be added to a particle dispersion, a polymer/monomer solution, or a mixture of inorganic particles and the polymer/monomer. As for the self-polymerizing linking agent, it is preferable to add the linking agent to the particle dispersion, so the linking agent is more likely to bond with the particle surface instead of undergoing a self-condensation reaction. For example, alkoxysilane can be hydrolyzed to a form capable of self-polymerization. The addition order and amount of the linking agent can affect the details of the composite structure formed. In particular, when reacting with inorganic particles, the linking agent is preferably sufficiently dispersed so that it can be more uniformly bonded to the inorganic particles.

[0228] In some embodiments, reaction conditions and/or the presence of a catalyst are required to initiate the reaction of the linking agent with the inorganic particles and/or the polymer/monomer. In these specific embodiments, the components may be mixed before adjusting the reaction conditions for adding the catalyst. Therefore, it is possible to form a well-mixed solution/dispersion to form a more uniform composite material before adjusting the reaction conditions or adding the catalyst.

[0229] Processing and Self-Assembly

[0230] After the polymer/inorganic particle composite is formed, the composite can be subjected to further processing. For the sake of convenience herein, the composite material refers to the structure of inorganic particles-linking agent-polymer/monomer that have been bonded in solution, dispersion, coating or solid form. For example, for the storage of the composite material and/or for the convenience of use, the properties (for example, concentration and solvent composition) of the solution/dispersion containing the composite material can be modified to facilitate further processing. Following the preferred specific embodiments described further below, the composite material can be incorporated into a specific structure or device in order to utilize the properties of the composite material. In order to facilitate the formation of localized devices, you can choose to have a composite material that facilitates self-organization

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The polymer can help self-assemble into a localized structure. The particles can be separated into one polymer phase or another phase of the composite material (wherein, due to the self-organization effect, different polymer phases can be identified), and the self-assembly structure can be formed from the self-assembly effect.

[0231] The composite forming solution/dispersion can be used directly in further processing. Alternatively, the composite material can be removed from the liquid, or the composite material can be placed in a different liquid. The liquid of the solution/dispersion can be changed by dilution, that is, different liquids are added to the solution/dispersion. If the composite material has sufficient molecular weight that can be retained by the dialysis tube, the liquid can be replaced by dialysis, or the liquid can be removed and used Displace the liquid to dissolve/disperse the composite material. Dialysis tubes with various pore sizes are commercially available. In order to replace the liquid, a liquid mixture can be formed, and then the original liquid can be removed by evaporation. If the liquid can form an azeotrope, the step of evaporation and removal is particularly effective. The method of removing the polymer/inorganic composite material from the liquid includes: evaporating the liquid, filtering or centrifuging the dispersion of the composite, or changing the properties of the solution/dispersion (for example, pH, liquid composition or ionic strength) to induce The composite settles from the liquid.

[0232] Generally, standard polymer processing techniques (which include heat treatment and solvent treatment methods) can be used to process composite materials. For example, the polymer/inorganic particle composite material can be formed into a structure through compression molding, injection molding, extrusion and calendering. In other words, the composite material can form a free structure, for example, a sheet. Likewise, certain techniques (for example, extrusion or drawing of a softened composite material) can be used to form the composite material into a fiber or a thin layer on the fiber. The solution/dispersion can be formed into a film/coating by spin casting and similar methods. The coatings formed have various parameters, including, for example, thin coatings with a thickness of less than about 1 micrometer.

[0233] In certain embodiments, the composite material forms a localized structure through self-assembly. The composition and/or structure of the composite material can be selected to promote the self-organization of the composite material itself. For example, block copolymers can be used to separate the different blocks of the polymer, which is a standard property of many block copolymers. Suitable block copolymers include, for example, polystyrene-block-polymethyl methacrylate, polystyrene-block-polyacrylamide, polysiloxane-block-polyacrylate, and mixtures thereof . These block copolymers can be modified to include suitable functional groups that can be bonded to linking agents. For example, the polyacrylate can be hydrolyzed or partially hydrolyzed to form an acid group. When the polymer is formed, if the acid group does not interfere with the polymerization reaction, all or part of the acrylate can be partially substituted by acrylic acid. Alternatively, the ester group in the acrylate may be substituted by an ester bond of a diol or an amide bond of a diamine, so that a functional group that can be bonded with a linking agent is still maintained. Block copolymers with many other blocks and other types of polymer components can be used.

[0234] The inorganic particles can be associated with only one polymer component in the block, so the inorganic particles can be separated together with the polymer component in the separated block copolymer. For example, the ABA diblock copolymer can only contain inorganic particles in the insert A, and the properties of inorganic particles can be used to make the separation of inorganic particles have functional advantages. Similarly, if the inorganic particles and the corresponding polymer have different solvation properties, the polymer and the bound inorganic particles can be separated by different blocks of similar block copolymers. In addition, the nanoparticle itself can be separated from the polymer to form a self-organized structure.

[0235] Other ordered copolymers include, for example, graft copolymers, comb copolymers, star block copolymers, dendrimers, mixtures thereof, and the like. All kinds of ordered copolymers can be regarded as a polymer blend in which the polymer components can be chemically bonded to each other. As described in the examples below, physical polymer blends can also be used, and they can also exhibit self-organization. The polymer blend contains a mixture of chemically different polymers. As described above with respect to block copolymers, the inorganic particles can be bonded to only a subset of the polymer species. Physical polymer blends can exhibit self-organization similar to block copolymers. The presence of the inorganic particles can fully change the properties of the composite material, so the interaction between the polymer and the inorganic particles can only physically interact with other polymer species that are different from the nascent polymer.

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[0236] Regardless of the mechanism of self-organization, some self-organizing composite materials contain nanoparticle related to the repetitiveness in the superstructure or supercrystalline structure. The particles may or may not be crystals themselves, and they will have the property of an ordered structure of the particles. As described further below, photo-induced crystallization can take advantage of these crystalline superstructures.

[0237] The self-organizing ability of the composite material is preferably used to form a self-assembled structure on the surface of the substrate. In order to bond the composite material to the surface, the polymer can simply be coated on the surface, or the composite material can form a chemical bond with the surface. For example, the polymer may include additional functional groups capable of bonding to one or more structures and/or one or more materials on the surface. These additional functional groups may be functional side groups selected to facilitate the self-assembly method.

[0238] Alternatively, the surface of the substrate may have a component (surface linking agent) capable of bonding with the polymer and/or the inorganic particles, so the composite material may be bonded to the surface via the polymer or the inorganic particles. For example, the substrate may include one or more functional groups (for example, halogens such as Br, CN, SCOCHs, SCN, COOMe, OH, COOH, SO3, COOCF3, olefinic positions such as vinyl, amine, thiol, sulfonate And combinations) of organic ingredients. Alternatively, the functional group of the surface linking agent may react with the unreacted functional group in the polymer. The suitable functional group in the surface linking agent that can be bonded to the polymer is equivalent to the functional group in the composite material linking agent that can be bonded to the polymer.

[0239] In some embodiments of self-assembly using nanoparticle, a part of the substrate surface has pores, which can be small holes, depressions, cavities, or the like. The pores can be arranged in an orderly or random arrangement. The size of the pores should be larger than the size of the nanoparticle. Although the preferred size of the pores and the density of the pores depend on the desired specific properties of the formed device, the diameter of the pores is generally less than 1 micrometer.

[0240] In order to deposit the composite material in the pores, the surface is contacted with a dispersion of the composite material. Then, the dispersion of the composite material is destabilized so that the composite material settles on the surface and enters the pores. The method of destabilizing the dispersion is as follows: changing the pH, for example, adjusting the pH to close to the isoelectric point; diluting the surfactant; or adding a co-solvent that can lead to a low-stability dispersion. After the desired amount of composite material is deposited, the dispersion is removed. Then, the composite material on the surface but not in the pores can be removed. For example, the surface can be gently rinsed with a dispersant to remove the composite material on the surface. Alternatively, the surface can be smoothed by polishing (for example, mechanical polishing or chemical-mechanical polishing). If a properly selected dispersant cannot effectively disperse the composite material, and if the washing step is not carried out thoroughly, it may be preferable to remove the composite material on the surface while leaving the composite material in the pores.

[0241] Anodized alumina or other metal oxides can be used to form a porous structure. Anodized alumina can form highly oriented and uniform pores. Placing the aluminum anode in a dilute acid (for example, sulfuric acid, phosphoric acid, or oxalic acid) solution can form fine pores in the anodized aluminum oxide. As aluminum is oxidized, porous alumina can be formed. The pore diameter can vary between at least 4 nanometers and 200 nanometers. The pores have a depth on the order of micrometers. The method of forming porous anodized alumina is described in the following materials: For example, D.A1-Mawlawi et al. Nano-wires formed in anodic oxide nanotemplates^，＞J. Materials Research, 9: 1014-1018 (1994) and D. Al-Mawlawi et al., Electrochemical fabrication of metal and semiconductor nano-wire arraysin Proc.Symp.Nanostructured Mater.Electrochem.,187th Meeting Electrochem Soc., Reno, NV,May21-26,1995.Electrochem. Soc.95(8): 262-273(1995) _o The method of using block copolymers to form ordered pores in silica and filling the pores to form photocrystals is described in Norris et al., US Patent No. 6,139,626 entitled "Three Dimensionally Patterned Materials and Methods For Manufacturing Same Using Nanocrystals" There is a description in the number (which is incorporated in this article for reference).

[0242] The method of forming multiple devices on the surface requires the effective components in the device to be localized within the specified limits related to the specific device. In order to localize the structure within specified boundaries through self-assembly, all procedures usually require a definable

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The method of the structure boundary and the method of using chemical affinity to associate the components of the device within the boundary of the separate self-assembly method. The method of defining the boundary usually uses external force to define the scope of the structure. The self-assembly method itself usually cannot define the structural boundary. Self-assembly is based on the natural sensing function of a composition/material that can form a natural regularity in the structure formed as a composition/material association. Although the nature of the processing steps may require a specific order, the localization step may be performed before or after performing the self-assembly method. Pure action can form a self-assembled structure that covers the compound/organic particle composite material in the corresponding range within the limit, and does not cover the area outside the limit.

[0243] The self-assembly within the activation boundary or the deactivation through the region outside the boundary can be used to couple the boundary-defining method and the self-assembly method respectively. Generally, an external force is applied to perform the activation or deactivation process. The localization can be done, for example, with a mask, etc., or using maskless lithography with focused radiation (for example, an electron beam, an ion beam, or a light beam).

[0244] The identification of a suitable activation or deactivation technique can be based on the specific self-assembly method used. The localization method usually includes activating the area used to lay out the self-assembled structure or deactivating a location separated from the selected location. In more detail, the localization method can isolate the regions where the self-assembled structure is formed. Suitable physical force or chemical materials can be used for activation/deactivation.

[0245] Various methods suitable for these purposes include, for example, conventional integrated circuit processing methods. Specifically, mask technology can be used to isolate the activation/deactivation boundary. Radiation or chemical action can be performed in the area defined by the mask. Likewise, a focused beam can be used for this localization. Suitable focused beams for obtaining surface modification include, for example, beams such as ultraviolet or X-rays; laser beams; electron beams or ion beams, which can be focused on selected areas for activation or deactivation. Suitable focusing methods are known in the art.

[0246] The activation method may include forming a specific material at a desired location, or removing a material or composition that inhibits self-assembly at the desired location. Specifically, a specific material can be formed within the boundary, and the specific material can cause the self-assembly method to occur within the boundary, while the surface material outside the boundary does not cause the self-assembly method. For example, a chemically active layer combined with the polymer may be formed within the boundary, and the surface of the substrate outside the boundary has different chemical functional groups that will not bond with the polymer. Likewise, a layer of inhibitory compound can be removed from the area within the boundary to expose a surface material that can be combined with the compound required by the self-assembly method, for example, a surface bonding agent. The inhibitory compound may be a photoresist compound, which in some cases can physically block the surface, and can be selectively removed before or after the self-assembly method is performed. The selected photoresist composition or other inhibitory compound can inhibit the self-assembly method. Therefore, the area covered by the inhibitory compound that surrounds the boundary area afterward does not participate in the self-assembly process.

[0247] Similarly, the area outside the boundary area can be deactivated. For example, a composition combined with the compound of the self-assembly method can be coated on the entire surface. Then, the composition can be removed from outside the defined area selected by the self-assembly method. Then, the self-assembly method is only performed in the defined area. In addition, an inhibitor material can be specifically deposited outside the boundary area, so the self-assembly method is only performed in the boundary area where the inhibitor material has been removed. Likewise, radiation can be used to deactivate or dissociate compounds outside the defined zone. The deactivation method can be performed using the above-mentioned mask and/or focusing method. As mentioned above, the layers can be processed to produce a three-dimensional overall structure.

[0248] The localization method used in conjunction with the self-assembly method is further described in Kambe et al., U.S. Patent Application Serial No. 09/558,266 entitled Self Assembled Structures cited in this application.

[0249] Use of composite materials

[0250] The polymer/inorganic particle composite material is suitable for effectively forming a device that can incorporate many materials. Preferably, the composite material can incorporate one or more of the various very uniform nanoparticles as described above. Selectively incorporate a specific composite material into a specific device, and due to the selectivity of the composite material, the device can obtain the desired function.

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[0251] In a preferred embodiment, the structure can form a microscopic configuration with two-dimensional or three-dimensional characteristics that can be integrated to form a complete object. The term "nano" is used to refer to the structure within each self-assembled device. The three-dimensional structure formed can form a superlattice or superstructure. Also, fibers formed of composite materials can be used, for example, as optical fibers or electronic or optoelectronic devices.

[0252] An example of the structure placed along the substrate of the combined polymer/inorganic particle composite is shown in FIG. 10. Referring to FIG. 10, the substrate 200 includes a structure or island structure 202, 204, 206, 208, 210, 212 made of composite materials. The integrated self-assembly structure is further described in the U.S. Patent Application Serial No. 09/558,266 named Self Assembled Structures by Kambe et al. cited in this application. Each composite material in the structures 202, 204, 206, 208, 210, 212 may include the same composition or different polymer compositions and/or inorganic particles as other structures. Preferably, the primary particles of the nanoparticle have a narrow particle size distribution, for example, the above-mentioned nanoparticle that can be formed by laser pyrolysis. Also, generally since a preferred particle dispersion is used, it is preferred that the nanoparticle has a small average secondary particle size.

[0253] Suitable devices that can incorporate nanoparticle or other self-assembled compositions include, for example, energy sources such as batteries; photocrystallization; active electronic or optoelectronic elements such as field emission devices; inactive elements such as electronic interconnectors, barriers Layer and insulation layer. Self-assembled electroactive particles can be used together with conductive particles to form electrodes. Likewise, conductive polymers and suitable inorganic particle-forming composite materials can be used to form the electrode.

[0254] Photo-induced crystallization is an ordered arrangement of composite material components, wherein the unit cell size of the photo-induced crystallization ranges from about one-quarter to about one optical wavelength. The refractive index of the material depends on the wavelength of the light. For example, the wavelength of visible light in the air is about 380 nanometers to about 780 nanometers. Generally, the size of the related photocrystal is about 100 nanometers to about 1000 nanometers. The particles can form crystalline superstructures with different refractive index ranges. The photocrystal can be formed from ordered arrangement of nano particles such as metal, silica, silicon nitride, silicon oxynitride, titanium oxide, or zinc oxide. Due to the size of the ordered arrangement, the photocrystal may have a spectral band gap that can prevent light from propagating in any direction. Therefore, photocrystals can be used to control self-emission and make light bends significantly, and self-assembly as described above can be used to form the orderly sequence.

[0255] Electrical interconnectors can be manufactured from conductive particles (for example, metal nanoparticle, such as silver and gold nanoparticle). Likewise, optical interconnectors allow light to be transmitted between devices. Materials with suitable refractive index can form an integrated optical interconnector. In order to transmit visible light, for example, silica, clay, and zinc oxide can be used. For example, a material with a higher refractive index can be used to form a barrier layer from silicon oxide particles. For example, the insulating layer can be formed from silicon dioxide nanoparticles. Field emission devices for displays can be doped with phosphorus particles, for example, zinc oxide or doped zinc oxide.

[0256] Refer to FIG. 11, which shows the coupler/distributor. The coupling/distributor 250 includes a coupling arm 252 and two branches 254. The coupler/distributor 250 can be used to connect multiple devices via electron conduction or light conduction. Suitable materials for electricity and light transmission are as described above.

[0257] Referring to FIGS. 12 and 13, a field effect transistor (FET) is shown_oThe FET 300 includes a source electrode 302, a drain electrode 304, a channel 306, and a gate electrode 308. Using the method described in this article, self-assembled materials are used to form one or more of the devices. In more detail, the electrodes 302, 304, and 308 can be formed using conductive metals as described above. The channel 306 can be formed from an electrically insulating material.

[0258] In more detail, the use of the polymer/inorganic particle composite material is especially used to form a device with a selective dielectric constant/refractive index. By controlling the refractive index, materials can be specifically designed for specific applications. Appropriate selection of refractive index is very important for the manufacture of electrical or optical materials. When there is no light loss, the refractive index is approximately the square root of the dielectric constant, so the manipulation of the refractive index is equivalent to the manipulation of the dielectric constant. Therefore, the refractive index/dielectric constant is related to the photoreaction and electrical response of a specific material. When designing optical or electrical interconnectors, refractive index manipulation is particularly important.

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[0259] As far as optical materials are concerned, the light transmission and optical properties at the interface directly depend on the choice of suitable refractive index. More specifically, the refractive and reflective optical properties of a material are directly related to the refractive index. For example, a high refractive index material can be used to form a microlens, which can focus light due to the light bending phenomenon at the interface of the material with a lower refractive index. These lenses can be called hierarchical index lenses. The light bending angle can be expressed according to Snell's law (msin0i=n2sin02, where ηι and Π2 are the refractive indices of related materials 1 and 2, and Ji and K are the relative angles). The imaginary part of the composite refractive index is related to light absorption.

[0260] In addition, the electrical properties of a material may also depend on the dielectric constant. For example, the capacitance of a material is directly proportional to the dielectric constant of the material. In order to reduce the capacitance of the electrical interconnector in the integrated circuit, it is better to have a low dielectric constant, preferably less than 2. Therefore, low-K materials are most suitable for making integrated circuits.

[0261] In addition, the time constant of the electrical reaction of a material is related to the dielectric constant. In order to react to the electric field, the conductive medium is usually brought close to the electrostatic equilibrium at a rate proportional to Μ (where t is the time, g is the constant, and K is the dielectric constant). Therefore, if K is larger, the conduction is slower to approach the equilibrium state. In the field effect transistor, it is best to have a high-K material adjacent to the channel. In the specific embodiment shown in FIGS. 12 and 13, the channel 306 can be connected to the source electrode 302 and the drain electrode 308. The use of K high material adjacent to the channel can reduce current leakage.

[0262] Since laser pyrolysis is a flexible method for synthesizing a variety of inorganic particles/powders, these particles can be selected to obtain the desired dielectric constant. Specifically, TiO2 generally has a high refractive index value ranging from about 2.5 to about 2.9. SiO2 generally has a low refractive index value of about 1.45 to about 1.5. The polymer generally has a low refractive index value of about 1.3 to about 1.6. The refractive index of the high refractive index composite material is preferably at least about 1.8. The refractive index of the low refractive index composite material preferably does not exceed about 1.5.

Example

[°263] Example 1-Formation of Titanium Oxide Particles

[0264] Rutile TiO2, anatase TiO2, and oxygen-deficient blue TiO2 particles can be prepared by laser pyrolysis. This reaction is carried out in a room equivalent to that shown in Figures 14-16.

14-16, the pyrolysis reaction system 400 includes a reaction chamber 402, a particle collection system 404, and a laser 406. The reaction chamber 402 includes a reactant inlet 414, which is located at the bottom of the reaction chamber 402 (where the reactant delivery system 408 is connected to the reaction chamber 402). In this embodiment, the reactant is transferred from the bottom of the reaction chamber, and the product is collected from the top of the reaction chamber.

[0266] Shield gas ducts 416 are located in front of and behind the reactant inlet 414. The inert gas is transferred into the shielding gas duct 416 through the vent 418. The shielding gas conduit guides the shielding gas along the inner wall of the reaction chamber 402 to prevent the reactant gas or product from combining with the inner wall.

[0267] The reaction chamber 402 extends along the line indicated by "w" in FIG. 14. The laser beam path 420 enters the reaction chamber through the window 422 (the main chamber 426 is replaced by the tube 424) and then passes through the extending direction of the reaction chamber 402. The laser beam passes through the tube 428 and exits the window 430. In a preferred embodiment, the tubes 424 and 428 replace the windows 422 and 430 at about 11 inches from the main chamber. The laser beam terminates at the beam collector 432. In operation, the laser beam traverses the reactant stream generated through the reactant inlet 414.

[0268] The top of the main chamber 426 leads to the particle collection system 404. The particle collection system 404 includes an outlet conduit 434 connected to the top of the main chamber 426 to receive the stream from the main chamber 426. The outlet conduit 434 carries product particles from the reactant stream to a cylindrical filter 436. The filter 436 has at one end thereof Cover 438. The other end of the filter 436 is fastened to the disc 440 firmly.

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The outlet 442 is fixed at the center of the disc 440 to provide a channel to the center of the filter 436. The outlet 442 is connected to the pump via a conduit. Therefore, in the stream flowing through the reaction chamber 402 to the pump, the product particles are trapped on the filter 436.

[0269] Titanium tetrachloride (Strem Chemical, Inc., Newburyport, MA) precursor vapor was added to the reaction chamber by bubbling Ar gas through the TiCh liquid in a container at room temperature. Use C2H2 gas as laser absorption gas and nitrogen as inert gas. Use 02 as the oxygen source. Add additional nitrogen as an inert diluent gas. The reactant gas mixture containing TiCOAr, 02 and C2 fields is guided into the reactant gas nozzle to be injected into the reactant chamber.

[0270] Representative reaction conditions for the preparation of rutile TiO2 particles and anatase TiO2 particles are shown in Table 1. In addition to positioning the particle collectors accordingly to facilitate the collection of products closer to the reaction zone, the rutile Ti02 particles (Ti0₂-l) Obtain blue hypoxic rutile Ti0 under the same conditions₂(Ti0₂-2)_oLow chamber pressure and low oxygen partial pressure result in a lack of oxygen in the produced TiO2. The slight heating of the particles in the air will cause the loss of blue color and form a rutile structure.

[0271] Table 1

[0272]

<td></td><td>Ti0₂-l</td><td>Ti0₂-3</td>

<td>phase</td><td>Rutile Ti02</td><td>Anatase Ti02</td>

<td>BET surface area (m2/g)</td><td>64</td><td>57</td>

<td>Stress)</td><td>110</td><td>150</td>

<td>Ar-dilution gas (slm)</td><td>4.2</td><td>8.4</td>

<td>Ar-Win(slm)</td><td>10.0</td><td>10.0</td>

<td>Ar-Sld.(slm)</td><td>2.8</td><td>2.8</td>

<td>Ethylene (slm)</td><td>1.62</td><td>1.25</td>

<td>Carrier gas-Ar-(Slm)</td><td>0.72</td><td>0.72</td>

<td>Oxygen (slm)</td><td>2.44</td><td>4.5</td>

<td>Laser Power-Entrance (Watts)</td><td>1400</td><td>1507</td>

<td>Laser power-outlet (watts)</td><td>1230</td><td>1350</td>

[0273] sccm = standard cubic centimeters per minute

[0274] slm=standard liters per minute

[0275] Argon-Win. = Nitrogen flowing through the inlet (490,492)

[0276] Argon-Sld. = Nitrogen flowing through tank (554,556)

[0277] The x-ray diffraction pattern of the product nanoparticle prepared under the conditions of Table 1 is shown in FIG. 17. Sample Ti0₂-l has an x-ray diffraction pattern equivalent to rutile TiO2. Sample Ti0₂-2 has similar Ti0₂-l X-ray diffraction pattern. Sample Ti0₂-3 has an x-ray diffraction pattern equivalent to anatase TiO2. The width of the peak in Fig. 17 shows that the crystallinity of sample 1 is lower than that of the other two samples. The sample Ti0₂Part of the peaks in the -l spectrum seem to be caused by the amorphous phase.

Example 2-Formation of particle suspension

[0279] This example illustrates that the titanium oxide nanoparticles prepared by the laser pyrolysis method as described in Example 1 form a fully dispersed diluent.

[0280] Each of the three TiO 2 particles described in Example 1 was used to form a suspension. Suspend these 3 kinds of granular powders in water, ethanol, DMSO, cyclohexane, cyclohexanone and phentydrone (1,2,3,4-tetrahydro9-drug). Ketone, THF). Use 9.75 milligrams (mg) of Ti02 powder in 13 grams of liquid to form 0.75% by weight TiO₂Suspension. Each sample was subjected to ultrasonic treatment in an ultrasonic bath for 2 hours. Then, the relative values of all the samples were measured in parallel by visual inspection.

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Sedimentation takes 2 weeks.

[0281] The results are shown in Table 2. After 2 weeks and several months of observation, the relative sedimentation of all samples is shown in parentheses, with a value of 1 representing the worst and a value of 7 representing the best.

[0282] Table 2

[0283]

<td>Solvent</td><td>Ti0₂-l</td><td>Ti0₂-2</td><td>Ti0₂-3</td>

<td>water</td><td>Very bad (3) 100% settlement</td><td>Very bad (1) 100% settlement</td><td>Very bad (2) 100% settlement</td>

<td>Cyclohexanone</td><td>Very good (4)~90% suspension</td><td>Very good (5) ~ 85% suspension</td><td>Excellent (7) ~ 100% suspension</td>

<td>Cyclohexane</td><td>Very bad (2) 100% settlement</td><td>Very bad (2) 100% settlement</td><td>Very bad (3) 100% settlement</td>

<td>Ethanol</td><td>Excellent (6) ~ 95% suspension</td><td>Good (4)&gt;75% settlement</td><td>Excellent(6)~90% suspension</td>

<td>THF</td><td>Excellent(5)~95% suspension</td><td>Excellent (7)&gt;30% settlement*</td><td>Very bad (4) ~ 100% settlement</td>

<td>DMSO</td><td>Very good (7) ~ 80% suspension*</td><td>Very good (6)&gt;50% settlement*</td><td>Inferior (5)&gt;70% settlement</td>

<td>Toluene</td><td>Very bad (1) 100% settlement</td><td>Very bad (3) 100% settlement</td><td>Very bad (1) 100% settlement</td>

[0284] *The suspended particles remain suspended for several months.

[0285] The use of cyclohexanone and ethanol can form an optimal suspension suitable for a short period of time (ie, after 2 weeks, the lowest observable sedimentation effect). THF can also sufficiently suspend one of the samples. Even after 2 weeks, these suspensions still showed no (or only a little) particle deposition. Observed after 2 weeks, the relative grade curve is shown in Figure 18 with the dielectric constant (K) as a variable. The diagram suggests that solvents/dispersants with medium polarity can give the best suspensions, while solvents with low or very high dielectric constants are not suitable.

[0286] The secondary particle size in the suspension was evaluated with a Horiba particle size analyzer (Horiba, Kyoto, Japan). The analysis of the particle size analyzer shows that all dispersants that can fully suspend the particles have good dispersibility/low agglomeration. Generally, all the suspended particles are in a size region below 80 nanometers, and the smaller the average particle size, the wider the distribution.

[0287] Since the detection limit of the particle size analyzer is 30 nanometers, an internal standard was used to evaluate the number of particles less than 30 nanometers in diameter. A commercially available Ti02 powder (R706 with AI2O3 coating, with an average particle size of 0.36 microns, and obtained from DuPont, Wilmington, DE) with good properties was mixed with the nanoparticle at a weight ratio of 1:1. The resulting suspension was analyzed with a Horiba particle size analyzer. Less than about 10% of the nanoparticle was observed. Therefore, most nanoparticle diameters are less than about 30 nanometers and cannot be detected by a particle size analyzer. However, the trend measured with this particle size analyzer indicates the degree of agglomeration. In particular, the use of a solvent that can sufficiently suspend particles can form a good dispersion.

[0288] Obtaining the absorption spectrum of an ethanol solution of titanium oxide particles at a concentration of 0.003% by weight_oTi0₂-l,Ti0₂-2 and mouth. The absorption spectra of the 23 samples are shown in Figures 19-21. For comparison, similar spectra were obtained from the ethanol dispersions of two commercially available Ti02 powders with a concentration of 0.0003% by weight, which are shown in Figure 22 and Figure 23, respectively. The first powder (Figure 22) was purchased from Alfa Aesar, Inc., Ward Hd 1, MA, and its average particle size was 0.17 microns. The second powder (Figure 23) was purchased from Aldrich Chemical Company, Makwaukee, WI, and had an average particle size of 0.26 microns.

[0289] The absorption spectrum of TiO2 in FIG. 23 shows that the bulk TiO2 in the visible part and the infrared part of the spectrum has a large absorption. On the contrary, the absorption spectrum of the powder in Figures 19-22 has very low absorption in the visible part and infrared part of the spectrum, but has enhanced absorption in the ultraviolet part. This shift and narrowing of the absorption spectrum is due to the decrease in the particle size. Compared with the powder that produces the spectrum of FIG. 22, the spectrum of the laser pyrolysis material in FIGS. 19-21 has lower visible light absorption and narrower and stronger ultraviolet absorption.

Example 3-Surface treatment of titanium oxide particles

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[0291] Aminopropyltriethoxysilane (APTES) was used as a silylation agent for surface treatment of these three kinds of TiO2 particles. APTES is believed to bind to the particles through the following reactions:

[0292] Particle-T i -0H+ ((CH3CH2O) 3-S i CH2CH2CH2NH2

[0293]-particles-Ti-0-Si (0CH₂C H3)2CH2CH₂CH₂NH2)

[0294] Further continuous hydrolysis of the ethoxy group can form additional Si bonds that are bound to the particles via a glutinous bond. The silylating agent can also undergo partial self-polymerization, especially if there is excess silylating agent and water.

[0295] According to the measured BET surface area of the particles, the amount of APTES relative to 1/2, 1, and 2 of the particle surface of the linking agent monolayer was calculated. An excess of the silylating agent can be added because not all of the silylating agent can be combined, and the silylating agent can undergo partial self-polymerization. In order to calculate the coverage, it is assumed that APTES is bonded to the particles perpendicular to the surface. Then, estimate the size of the molecule. This calculation method only provides a rough estimate of the coverage. As described below, it has been experimentally found that the coverage on the particle surface can be higher than the coverage estimated from these calculation results.

[0296] Experiments were performed to check the particle coating. As described in the examples below, these silylated particles are then used to form polymer composites. In forming these composite materials, the polymer reacts with the coating film particles without removing the coating film particles from the solution. Ethanol is used as the solvent because a related polymer (polyacrylic acid) is more soluble in ethanol than in cyclohexanone. In addition, ethanol has good water absorption, and the moisture helps the hydrolysis of the ethoxy group.

[0297] In order to prepare the silylated particles, a solution of APTES was prepared in fresh ethanol containing trace amounts of water, the amount of which was suitable for 50% coverage, 100% coverage and 200% coverage. Based on the assumption that some reagents will remain in the solution and that the calculated coverage value is only a rough estimate, another reagent is used. Prepare to have 100 mg Ti0 on the outside of the drying box₂-Small glass bottles of 3 and 4 grams of solution to absorb water. However, long-term exposure to water must be avoided, and after adding the solvent, the vial must be sealed. The sealed vial was ultrasonically treated and then left to stand for about 72 hours.

[0298] The powder was deposited on the bottom of the vial. Use a pipette to remove the supernatant (that is, the solution above the settled particles), and then add new ethanol. Next, the powder is sufficiently suspended. It has been found that the supernatant contains unreacted silylating agent. In each sample made of APTES whose estimated amount satisfies 50% coverage, 100% coverage, and 200% coverage, the original APTES percentages with the removal of the supernatant are 44.7%, 27.8%, and 32.4, respectively %. Therefore, in terms of the coverage of APTES on the particles, the calculated estimate seems to be low, because when the initial solution has an estimated amount suitable for 200% coverage and the recovery is less than 50%, more than 100% coverage can be obtained. range.

[0299] The interaction of the suspended silylated particles with polyacrylic acid is described in the following examples.

Example 4-Formation of poly(acrylic acid)/titanium oxide particle composite

[0301] This example illustrates the formation of poly(acrylic acid) and Ti0₂-3 Powder and method of composite material based on silane-based linking agent. In these studies, the fully suspended APTES-coated TiO described in Example 3 was used.₂-3 particles.

[0302] The polyacrylic acid is believed to be capable of forming an amide bond by reacting the acid group with the primary amine of the silylating agent. The first interaction of the polymer and the surface-treated particles involves the formation of a salt with the primary amine and an acid. Then, at a temperature of 140°-160°, the salt unit condenses to form an amide bond. The diagram of the reaction is as follows:

[0303] Polymer-C00H+H2N-Si-0-Τ i-particles-

[0304] Polymer-CONH---Si-0-Ti-particles.

[0305] The infrared absorption band of the Fourier transform infrared spectrum of the composite material is at 1664 cm, which is the frequency characteristic of the amide bond. Use 2000MW polymer and twice the amount of single layer Ti0₂The infrared absorption spectrum of the composite material formed by the -3 particles is shown in A in Figure 24. The corresponding spectrum of the composite material formed by using unmodified particles is shown in Figure 24, B. The infrared absorption spectrum of this polymer without using any titanium oxide particles is shown by symbol C in FIG. 24. Spectra B and C are missing in Figure 24

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Lack of the amide absorption band.

[0306] Spectrum A in FIG. 24 relates to a composite material processed at 160°C after combining the components. This spectrum is also indicated by A in FIG. 25. The spectrum of the composite material treated at 120°C (indicated by B in Figure 25) shows less obvious amide bond formation. The spectrum of the composite material treated at 230°C (indicated by C in Figure 25) shows an increase in the amide bond structure.

[0307] Two different polymer molecular weights and two different particle loadings were used to form composite materials. Poly(acrylic acid) (PAA) is also added to the dispersion of particles that have not been modified by the silylating agent. The suspended particles are divided into equal samples to form different composite materials. Using 1 equivalent weight of PAA per part of titanium oxide particles to make a higher particle-filled sample, it can produce a composite material with 50% by weight of particles. Using 9 equivalents of PAA per part of titanium oxide particles to make a lower particle-filled sample, it can produce a composite material with 10% by weight of particles. The average molecular weight of the low molecular weight polymer is 2,000 Daltons, and the average molecular weight of the high molecular weight polymer is 250,000 Daltons. Therefore, functionalized Ti0 is used₂-3 pellets are made into a total of 4 samples, and untreated Ti0 is used₂-3 pellets were made into 4 kinds of control samples.

[0308] Once the composite material is used as a coating, it can be found that the microstructure of the sample formed by using the processed particles and the sample formed by using the untreated particles are significantly different. Place drops on the surface to form the coating. The drop can cover the surface and allow it to dry. Further analysis of the dry composite material. In particular, the functionalized particles can form a smoother material than the non-functionalized particles. Similarly, it can be found that there is a significant difference between the sample made using the high molecular weight polymer and the sample made using the low molecular weight polymer. Lower molecular weight polymers can form smoother materials.

[0309] Scanning electron micrographs (SEM) can be obtained with coatings formed from silylated particles and composite materials with untreated particles, respectively. The SEM photographs of silylated (ie, treated) particles with 10% particle loading (with 2000MW polymer) and untreated particles at two magnifications are shown in Figures 26-29, respectively. Composites with processed particles (Figures 26 and 27) seem to produce a smoother and more uniform material than composites formed with untreated particles (Figures 28 and 29). Similarly, the two magnified SEM photographs of the composite material with processed and unprocessed particles (with a particle filling content of 50% by weight) are shown in Figures 30-33, respectively. Coatings with treated particles (Figures 30 and 31) can form a smooth and uniform coating, while composite materials with untreated particles (Figures 32 and 33) show agglomeration and rough surfaces.

[0310] Similar photographs of composite materials formed using polymers with a molecular weight of 250,000 Daltons can be obtained. The SEM photographs of the composite material with 10% by weight particles filled are shown in Figures 34-37 at two magnifications. It has been found that composites with treated particles (Figures 34 and 35) have much lower agglomeration than composites with untreated particles (Figures 36 and 37). The SEM photos of the composite material with a filling content of 50% by weight are shown in Figures 38-41. Furthermore, the composites formed using the processed particles (Figures 38 and 39) can form a more uniform and low-agglomerated film than the composites formed using the untreated particles (Figures 40 and 41).

[0311] Differential scanning calorimetry was used to check the thermal stability of the composite material. First, dry the sample under high vacuum at 600°C. (1) 50% filled Ti02 and PAA (2000MW) modified by silane linker, (2) unmodified Ti02 and PAA (2000MW) filled with 50%, (3) PAA cured from ethanol ( 2000MW), and (4) the results of PAA (2000MW) obtained from the manufacturer are shown in the curve in Figure 42. The composite material formed by the self-functionalized particles has significantly higher thermal stability.

[0312] Example 5-Evidence that the addition of polyethylene glycol may cause self-organization

[0313] The composite material formed by the silylated functional TiO 2 particles and PAA described in Example 4 was further mixed with polyethylene glycol to check the structure formed.

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[0314] The TTI02-PAA composite material of Example 4 (with 50% (1:1) Ti0₂Filled amount of PAA (2000MW)) is blended with polyethylene glycol (PEG). The blend contains 90% by weight PEG and 10% by weight TiO₂-PAA composite material. Drop the composite material onto the surface and dry the material to form the PEG-TiO₂-PAA composite material coating. Alternatively, the composite material can be cast into a film. These two methods get the same result. For comparison, a polymer blend is formed that does not have TiO2 particles at all. These polymer blends can form sticky surfaces without forming smooth surfaces.

[0315] When untreated TiO2 particles are used to form the composite material, after adding the PEG, the resulting mixture has uniformly dispersed particles in the polymer film. Some random particles can be seen visually, and a slight peeling phenomenon can be found. However, when a composite material with the silylated functional particles is used, there is a phenomenon of separation into domains. Specifically, a clear stripe pattern can be found. The function of this organization as a geometric pattern can provide direct evidence of self-organization.

[0316] Example 6-Composite material of polyamide

[0317] This embodiment includes a method of forming a titanium oxide/nylon composite material. These composite materials can be formed by reacting silylated titanium oxide particles with 6-amino-hexanoic acid. This example illustrates the simultaneous polymerization of these organic substances and the formation of the composite material.

[0318] 6-Amino-hexanoic acid can self-polymerize to form polyamides. After the self-polymerization reaction, the formed polyamide coating can form a feather-like fine pattern. The corresponding SEM micrographs (two magnifications) of the polymer without any titanium oxide particles are shown in Figures 43 and 44. If untreated particles are used to form a composite material with the polyamide, the particles will separate within the polymer and will not form a uniform composite material. In the SEM micrographs of Figures 45 and 46 (two magnifications) This phenomenon can be clearly seen. The basic structure of the material can form a pattern similar to that formed by the single polyamide polymer. However, if you use Ti0 that has been treated (that is, silylated)₂When the -3 particles form a composite material, the crystalline pattern formed by the composite material is different from the crystalline pattern formed by the polymer alone. Specifically, the pattern formed by the composite material has long-range order, multiple branches, and order on different scales. The SEM photographs (two magnifications) of the composite material with a particle loading of 50% by weight are shown in Figures 47-48, which indicate the incorporation of the particles in a highly ordered structure.

[0319] Example 7-Composite material of adipic acid

[0320] This example illustrates a method of forming a composite material from a monomer unit. In this case, the monomer itself is not polymerized. The monomer interacts with the functionalized TiO2 particles to form a polymer, where the particles themselves can form a star bond within the overall polymer structure.

[0321] The monomer unit is adipic acid, H00C(CH₂)6C00H_oEach acid functional group of the adipic acid can be combined with the primary amine of the silylating agent. Therefore, the adipic acid and the silylated particles are used as monomer units in the final polymer to form a network polymer, and the silylated particles can be used as the monomer units of the final polymer. Fourier transform infrared measurement confirmed that the adipic acid formed an amide bond when reacting with the functionalized particles. The infrared spectrum of the composite material of the silylated particles (A) with amide bonds and the untreated particles (B) is shown in Figure 49.

[0322] The TiO2-polymer composite formed by using untreated TiO2 particles can form a uniform coating without a pattern. In the composite material formed by using silylated TiO2 particles, the aggregation phenomenon of particles forming a single band can be seen visually, that is, the single band can be clearly seen during inspection.

[0323] The above-mentioned specific embodiments are for illustration rather than limitation. Other specific embodiments still fall within the scope of the claims. Although the present invention has been described with preferred specific embodiments, those skilled in the art will understand that the form and details of the present invention can be changed as long as it does not violate the concept and scope of the present invention.

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