Plasma deposition process with removal of substrate tube
Abstract
Process for manufacturing a precursor for a primary preform for optical fibers by means of an internal plasma deposition process, the process of which comprises the steps of: i) providing a hollow substrate tube; ii) creating inside said hollow substrate tube a first plasma reaction zone having first reaction conditions by means of electromagnetic radiation to effect the deposition of unglazed silica layers on the inner surface of said hollow substrate tube , and subsequently; iii) creating inside said hollow substrate tube a second plasma reaction zone having second reaction conditions by means of electromagnetic radiation to effect the deposition of vitrified silica layers on the unglazed silica layers deposited in the stage ii); iv) remove the hollow substrate tube from the vitrified silica layers deposited in stage iii) and from the vitrified silica layers deposited in stage ii) to obtain a deposited tube.
Term
7.7 yearsto projected expiry
Projected expiry 5 June 2034, counted from filing; an application has no term until it is granted.
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14 claims: 10 independent, 4 dependent
- 1ES 2 646 945 T3 REIVINDICACIONES 1. Procedimiento para fabricar un precursor para una preforma primaria para fibras ópticas por medio de un proceso de deposición de plasma interno, cuyo procedimiento comprende las etapas de:i) proporcionar un tubo de substrato hueco;ii) crear en el interior de dicho tubo de substrato hueco una primera zona de reacción de plasma que tiene primeras condiciones de reacción por medio de radiación electromagnética para efectuar la deposición de capas de sílice sin vitrificar sobre la superficie interna de dicho tubo de substrato hueco, y posteriormente;iii) crear en el interior de dicho tubo de substrato hueco una segunda zona de reacción de plasma que tiene segundas condiciones de reacción por medio de radiación electromagnética para efectuar la deposición de capas de sílice vitrificada sobre las capas de sílice sin vitrificar depositadas en la etapa ii);iv) eliminar el tubo de substrato hueco de las capas de sílice vitrificada depositadas en la etapa iii) y de las capas de sílice sin vitrificar depositadas en la etapa ii) para obtener un tubo depositado.
- 2Procedimiento de acuerdo con la reivindicación 1, que comprende una etapa adicional v) llevada a cabo después de la etapa iv), consistiendo la etapa v) en someter el tubo depositado obtenido en la etapa iv) a un tratamiento de colapsado para formar una preforma primaria.
- 3Procedimiento de acuerdo con la reivindicación 1 o 2, que comprende una etapa adicional vi) llevada a cabo después de la etapa iv) o de la etapa v) consistente en:proporcionar externamente a dicho tubo depositado de la etapa iv) o dicha preforma primaria de la etapa v) con una cantidad adicional de vidrio.
- 4Procedimiento de acuerdo con una cualquiera de las reivindicaciones precedentes, en el que durante la etapa iv) el tubo de substrato es eliminado mecánicamente.
- 5Procedimiento de acuerdo con una cualquiera de las reivindicaciones precedentes, en el que las primeras condiciones de reacción comprenden una presión superior a 30 milibares, preferiblemente superior a 60 milibares.
- 6Procedimiento de acuerdo con una cualquiera de las reivindicaciones precedentes, en el que las primeras condiciones de reacción comprenden una presión inferior a 1000 milibares, preferiblemente inferior a 200 milibares.
- 7Procedimiento de acuerdo con una cualquiera de las reivindicaciones precedentes, en el que las segundas condiciones de reacción comprenden una presión de entre 1 y 25 milibares, preferiblemente entre 5 y 20 milibares, más preferiblemente entre 10 y 15 milibares.
- 8Procedimiento según una cualquiera de las reivindicaciones precedentes, en el que como tubo de substrato proporcionado en la etapa i) se utiliza un tubo de substrato que no es de cuarzo, preferiblemente un tubo de substrato de alúmina.
- 9Procedimiento de acuerdo con una cualquiera de las reivindicaciones precedentes, en el que en la etapa ii) se depositan entre 1 y 500 capas de sílice sin vitrificar.
- 10Procedimiento de acuerdo con una cualquiera de las reivindicaciones precedentes, en el que las capas de sílice sin vitrificar tienen cada una, independientemente, un espesor de entre 1 y 5 micrómetros, preferiblemente de entre 2 y 3 micrómetros.
- 11Procedimiento de acuerdo con una cualquiera de las reivindicaciones precedentes, en el que las capas de sílice sin vitrificar que se depositan en total tienen un espesor de entre 1 y 1000 micrómetros.
- 12Procedimiento de acuerdo con una cualquiera de las reivindicaciones 1 o 3 a 11, en el que el precursor para una preforma primaria es un tubo de substrato.
- 13Procedimiento de acuerdo con una cualquiera de las reivindicaciones 1 o 3 a 11, en el que el precursor para una preforma primaria se utiliza como tubo de substrato para la fabricación de una preforma primaria por medio de un proceso de deposición interna asistida por plasma.
- 14Procedimiento de acuerdo con una cualquiera de las reivindicaciones precedentes, en el que la radiación electromagnética utilizada son microondas. ES 2 646 945 T3 REFERENCIAS CITADAS EN LA DESCRIPCIÓN La lista de referencias citada por el solicitante lo es solamente para utilidad del lector, no formando parte de los documentos de patente europeos. Aún cuando las referencias han sido cuidadosamente recopiladas, no pueden 5 excluirse errores u omisiones y la OEP rechaza toda responsabilidad a este respecto. Documentos de patente citados en la descripción • US 4314833 A[0011] • EP 0554845 A[0015] • WO 9935304 A [0012] • US 6988380 B [0016]
Independent claims14
133 paragraphs in 3 sections, as filed
ES 2 646 945 T3
DESCRIPTION
Process for plasma assisted deposition with removal of the substrate tube
[0001] The present invention relates to a process for manufacturing a precursor for a primary preform for optical fibers by means of a plasma-assisted internal deposition process such as a plasma-assisted chemical vapor deposition (PCVD) process. internal. The present invention further relates to a process for manufacturing a primary preform for optical fibers by means of a plasma-assisted internal deposition process.
[0002] The present invention relates to the field of optical fibers. More specifically, it relates to the field of manufacturing optical fibers by chemical vapor deposition. There are several known types of chemical vapor deposition (CVD), such as external vapor deposition (OVD), axial vapor deposition (VAD), modified chemical vapor deposition (MDVD), and chemical deposition. plasma-assisted enhanced vapor phase (PECVD or PCVD). Plasma-assisted chemical vapor deposition (PECVD or PCVD) is a process used to deposit thin films from a gaseous state (vapor) to a solid state on a substrate. During the process chemical reactions are involved that occur after the creation of a plasma of the reactive gases.
[0003] Generally, in the field of optical fibers, multiple thin films of glass are deposited on the inner surface of a substrate tube. The substrate tube is hollow to allow internal deposition. The substrate tube may be glass, preferably quartz glass (SiO<sub>2</sub>). Glass-forming gases (namely, reactive gases comprising glass-forming gases and optionally dopant precursors) are introduced into the substrate tube from one end (referred to as the supply side of the substrate tube). The doped or undoped glass layers (depending on the use of reactive gases with or without one or more dopant precursors, respectively) are deposited on the inner surface of the substrate tube. The remaining gases are discharged or removed from the other end of the substrate tube; This is called the discharge side of the substrate tube. Removal is optionally carried out by means of a vacuum pump. The vacuum pump has the effect of generating a reduced pressure inside the substrate tube, the reduced pressure of which generally comprises a pressure value ranging from 5 to 50 millibars.
[0004] Generally, plasma is induced, using electromagnetic radiation, eg microwaves. Generally, electromagnetic radiation from a generator is directed to an applicator through a waveguide, which applies it around the substrate tube. The applicator couples electromagnetic energy to a plasma that is generated within the substrate tube. The applicator is reciprocally displaced in the longitudinal direction of the substrate tube. Therefore, the formed plasma, also called the plasma reaction zone, also moves reciprocally. As a result of this movement, a thin layer of vitrified silica is deposited inside the substrate tube with each pass or stroke.
[0005] During the plasma deposition process, the applicator and the substrate tube are generally surrounded by an oven to maintain the substrate tube at a temperature between 900 ° C and 1300 ° C.
[0006] In this way, the applicator travels in translation along the substrate tube within the limits of a furnace surrounding the substrate tube and the applicator reciprocating within the furnace. With this translational movement of the applicator, the plasma also moves in the same direction. When the applicator reaches the inner wall of the oven near one end of the substrate tube, the motion of the applicator is reversed so that it travels toward the other end of the substrate tube toward the other inner wall of the oven. The applicator, and therefore the plasma, reciprocates along the substrate tube. Each round trip is called a pass or run. With each pass, a thin layer of vitrified silica material is deposited on the inside of the substrate tube.
[0007] This plasma produces the reaction of glass-forming gases (for example, O2, SiCU and, for example, a precursor of a dopant, such as GeCl4 or other gases) that are supplied to the interior of the substrate tube. The reaction of the glass-forming gases allows the reaction of Si (silicon), O (oxygen) and for example the dopant Ge (germanium) to effect the direct deposition of, for example, Ge-doped SiOx on the internal surface of the substrate tube.
[0008] Normally, a plasma is generated only in a part of the substrate tube, that is, the part that is surrounded by the applicator. Applicator dimensions are smaller than oven and substrate tube dimensions. Only in the plasma position, the reactive gases turn into solid glass and settle on the inner surface of the substrate tube. As the plasma reaction zone travels along the substrate tube, the glass is deposited more or less uniformly along the substrate tube. [0009] As the number of passes increases, the accumulated thickness of these thin films, that is, of the deposited material, increases; which leads to a decrease in the remaining internal diameter of the substrate tube. In other words, with each pass the hollow space within the substrate tube becomes smaller and smaller.
[0010] After the vitrified silica layers have been deposited inside the substrate tube, said substrate tube is subsequently contracted by heating into a solid rod (collapsed). The resulting solid rod is called a primary preform. In a special embodiment, the solid rod or primary preform can also be externally provided with an additional quantity of glass, for example, by an external vapor deposition process or on direct glass coating (referred to as envelope
ES 2 646 945 T3 coating) or using one or more preformed glass tubes (called jacketing), thus obtaining a composite preform called final preform. From the final preform produced in this way, one end of which is heated, the optical fibers are obtained by drawing in a drawing tower. The refractive index profile of the consolidated (final) preform corresponds to the refractive index profile of the optical fiber drawn from said preform.
[0011] A way of manufacturing an optical preform by means of a PCVD process is known from US Patent No. 4,314,833. According to the process known from that document, one or more layers of doped or undoped glass are deposited inside a substrate tube, using a low pressure plasma in the substrate tube.
[θ0ΐ2] According to international application WO99 / 35304, microwaves from a microwave generator are directed towards an applicator through a waveguide, the applicator of which surrounds a substrate tube. The applicator couples the high frequency energy into the plasma.
[0013] The substrate tube is incorporated into the optical fiber produced. The layers of glass deposited on the inside of the hollow substrate tube, the hollow substrate tube itself, and the layers of glass deposited on the outside of the hollow substrate tube or the primary preform are incorporated into the resulting final preform and after stretching. they are present in the optical fiber produced.
Examples of prior art documents disclosing the overcoating process are as follows. In each of these documents, the substrate tube is incorporated into the final preform.
[0015] EP 0554845 provides an overcoating process in which deposition of glass inside a hollow substrate tube is prevented.
[0016] US 6,988,380 describes a PCVD process for overcoating in which deposition of glass inside the hollow substrate tube is prevented.
[0017] A disadvantage of incorporating the substrate tube into the produced optical fiber is that high quality substrate tubes are required which also have high temperature tolerance and good adhesion to the deposited glass material. For this reason, a quartz glass substrate tube is often used in the prior art.
However, the present inventors have observed that the purity of such commercially available quartz tubes is not always sufficient. Furthermore, the general geometric properties of these tubes are not always satisfactory.
[0019] Another disadvantage of incorporating the substrate tube into the produced optical fiber is the limitation in the refractive index profiles of the optical fibers that are produced. If, for example, an optical fiber having a depressed trench (i.e. negative refractive index relative to silica) is desired directly surrounded by a depressed outer optical coating, this would require a substrate tube with an index difference negative refraction with respect to that of silica. This can, for example, be obtained using a tube of fluorine doped silica substrate. However, these tubes are difficult to produce and very expensive. In addition, they are softer than undoped silica substrate tubes, making them more difficult to use in deposition processes and more prone to breakage and deformation during the process. [0020] If, on the other hand, a fiber optic profile having an external optical coating with a positive refractive index profile with respect to silica is desired, a tube of doped (eg, doped) silica substrate is required with germanium). Such a tube is difficult to produce, very expensive and, furthermore, almost impossible to process by current standard techniques.
Therefore, there is a need for an alternative solution to the above problem.
[0022] It is an object of the present invention to provide a process for manufacturing a preform for optical fibers that allows greater flexibility in the refractive index of the final preform.
[0023] It is another object of the present invention to provide a process that eliminates the use of high quality substrate tubes.
[0024] It is another object of the present invention to provide a process that allows the use of substrate tubes other than quartz.
[0025] One or more of these objects is achieved by the present invention.
Summary of the invention
The present invention relates, in a first aspect, to a process for manufacturing a precursor primary main preform for optical fibers by means of a plasma-assisted internal deposition process. During this process, the substrate tube is removed from the layers deposited within it.
This process according to a first aspect of the present invention comprises the steps of:
i) providing a hollow substrate tube;
ii) creating inside said hollow substrate tube, a first plasma reaction zone having first reaction conditions by means of electromagnetic radiation to effect the deposition of ungitrified silica layers on the internal surface of said substrate tube hollow, and later;
iii) creating inside said hollow substrate tube, a second plasma reaction zone having second reaction conditions by means of electromagnetic radiation to effect the deposition of vitrified silica layers on the ungitrified silica layers deposited in the stage ii);
iv) removing the hollow substrate tube from the layers of vitrified silica deposited in step iii) and from the unglazed silica layers deposited in step ii) to obtain a deposited tube.
Said deposited tube is a precursor to a primary preform. Said deposited tube is in fact the
ES 2 646 945 T3 layers of material deposited within said substrate tube but without the substrate tube. Said primary preform can be obtained by collapsing said deposited tube, either directly or after a step of externally providing extra glass. See also the third aspect below.
In another aspect, the precursor for a primary preform obtained (viz. The deposited tube) is used as a substrate tube in a subsequent deposition process. In other words, according to this embodiment, the present invention relates to a new process for the production of a substrate tube. Therefore, in this aspect, the precursor for a primary preform is a substrate tube.
In this aspect, the present invention refers to a method for manufacturing a substrate tube for optical fibers by means of a plasma-assisted internal deposition process, which method comprises the steps of: i) providing a substrate tube gap; ii) creating inside said hollow substrate tube a first plasma reaction zone having first reaction conditions by means of electromagnetic radiation to effect the deposition of ungitrified silica layers on the internal surface of said hollow substrate tube , Y; subsequently iii) creating inside said hollow substrate tube a second plasma reaction zone having second reaction conditions by means of electromagnetic radiation to effect the deposition of vitrified silica layers on the unglazed silica layers deposited in the stage ii); and iv) removing the hollow substrate tube from the vitrified silica layers deposited in step iii) and from the unglazed silica layers deposited in step ii) to obtain a substrate tube.
In a second aspect, the present invention relates to a method for removing a substrate tube from layers of vitrified silica deposited on its internal surface by means of a plasma-assisted internal deposition process. The process of this second aspect comprises steps i) to iv) above.
[0032] In a third aspect, the present invention refers to a process for manufacturing a primary preform for optical fibers by means of a plasma-assisted internal deposition process, the process of which comprises the steps of:
i) providing a hollow substrate tube;
ii) creating inside said hollow substrate tube, a first plasma reaction zone that has first reaction conditions by means of electromagnetic radiation to effect the deposition of ungitrified silica layers on the internal surface of said substrate tube hollow, and subsequently, iii) creating inside said hollow substrate tube, a second plasma reaction zone having second reaction conditions by means of electromagnetic radiation to effect the deposition of vitrified silica layers on the ungitrified silica layers deposited in step ii), iv) eliminate the hollow substrate tube from the layers of vitrified silica deposited in step iii) and of the unglazed silica layers deposited in step ii) to obtain a deposited tube.
v) subjecting the deposited tube obtained in step iv) to a collapse treatment to form a primary preform.
[0033] Hereinafter, different embodiments of the present invention are described.
These embodiments are, unless otherwise indicated, applicable to all aspects of the present invention.
In one embodiment, the hollow substrate tube has a supply side and a discharge side.
[0036] In another embodiment, during step ii) of deposition of unglazed silica layers, a gas flow is supplied inside said hollow substrate tube.
In another embodiment, during step iii) of depositing vitrified silica layers a gas flow is supplied into said hollow substrate tube.
[0038] In another embodiment, a gas flow is supplied into said hollow substrate tube before step ii) of deposition of unglazed silica layers.
[0039] In another embodiment, after step iii) of depositing vitrified silica layers a gas flow is supplied into said hollow substrate tube.
In another embodiment, the gas flow is supplied into said hollow substrate tube through the supply side thereof.
In another embodiment, the gas flow supplied during step ii) comprises at least one glass-forming gas.
In another embodiment, the gas flow supplied during step iii) comprises at least one glass-forming gas. During this stage iii) it is possible that the composition of the gas flow changes with each pass. This is revealed in more detail below.
[0043] In another embodiment, the gas flow supplied before step ii) comprises oxygen in order to create suitable conditions for the creation of a plasma.
[0044] In another embodiment, the gas flow supplied after step iii) comprises oxygen. This gas flow supplied after step iii) is used to remove any residue and unwanted from the deposited tube obtained, for example gases containing chlorine.
[0045] In another embodiment, said first reaction zone moves back and forth along the longitudinal axis of said hollow substrate tube between an inversion point located close to the supply side and an inversion point located close to the discharge side of said hollow substrate tube. According to this embodiment, after step ii) a substrate tube is obtained having unglazed silica layers deposited on its inner surface.
In another embodiment, said second reaction zone reciprocates along the longitudinal axis
ES 2 646 945 T3 of said hollow substrate tube between a reversal point located close to the supply side and a reversal point located close to the discharge side of said hollow substrate tube. According to this embodiment, after step iii) a substrate tube is obtained having unglazed silica layers deposited on its internal surface in step ii) and vitrified silica layers deposited on the unglazed layers in step iii ) on its inner surface.
[0047] In another embodiment, the process according to the present invention comprises a further step v) carried out after step iv). In this stage v) the deposited tube obtained in stage iv) is subjected to a collapse treatment to form a primary preform.
In another embodiment, the process according to the present invention comprises an additional step vi). This step can be carried out after step iv), that is, in the deposited tube or after step v), that is, in the primary preform. This step vi) refers to externally providing said deposited tube or said primary preform with an additional quantity of glass.
In another embodiment, the following order of steps is followed:
i) providing a hollow substrate tube;
ii) creating inside said hollow substrate tube a first plasma reaction zone having first reaction conditions by means of electromagnetic radiation to effect the deposition of ungitrified silica layers on the internal surface of said hollow substrate tube , and subsequently;
iii) creating inside said hollow substrate tube a second plasma reaction zone that has second reaction conditions by means of electromagnetic radiation to effect the deposition of vitrified silica layers on the ungitrified silica layers deposited in the step ii);
iv) removing the hollow substrate tube from the layers of vitrified silica deposited in step iii) and from the unglazed silica layers deposited in step ii) to obtain a deposited tube;
v) subjecting the deposited tube obtained in step iv) to a collapse treatment to form a primary preform;
vi) externally provide said primary preform obtained in step v) an additional quantity of glass to obtain a final preform.
In another embodiment, when step vi) has been carried out in the deposited tube obtained in step iv), step v) can be carried out after step vi). Therefore, in this embodiment, the order of stages is as follows:
i) providing a hollow substrate tube;
ii) creating inside said hollow substrate tube a first plasma reaction zone having first reaction conditions by means of electromagnetic radiation to effect the deposition of ungitrified silica layers on the internal surface of said hollow substrate tube , and subsequently;
iii) creating inside said hollow substrate tube a second plasma reaction zone that has second reaction conditions by means of electromagnetic radiation to effect the deposition of vitrified silica layers on the ungitrified silica layers deposited in the step ii);
iv) removing the hollow substrate tube from the layers of vitrified silica deposited in step iii) and from the unglazed silica layers deposited in step ii) to obtain a deposited tube;
vi) externally provide on said deposited tube obtained in step iv) an additional quantity of glass;
v) subjecting the deposited tube provided externally with glass obtained in step vi) to a collapse treatment to form a primary or final preform.
[0051] In another embodiment, during step iv) the substrate tube is mechanically removed. Therefore, in this embodiment, the substrate tube is mechanically removed.
In another embodiment, the first reaction conditions comprise a pressure greater than 30 millibars, preferably greater than 40 millibars, more preferably greater than 50 millibars, even more preferably greater than 60 millibars.
In another embodiment, the first reaction conditions comprise a pressure of less than 1000 millibars, preferably less than 800 millibars, more preferably less than 600 millibars, even more preferably less than 400 millibars, or even less than 200 millibars.
In another embodiment, the second reaction conditions comprise a pressure of between 1 and 25 millibars, preferably between 5 and 20 millibars, more preferably between 10 and 15 millibars.
[0055] In another embodiment, the substrate tube provided in step i) is a non-quartz substrate tube, preferably an alumina substrate tube.
In another embodiment, in step ii) between 1 and 500 layers of unglazed silica are deposited. Depending on the type of mechanical removal used, there are different preferred ranges for the number of unglazed silica layers. This is explained in more detail below.
[0057] In another embodiment, the unglazed silica layers each independently have a thickness of between 1 and 5 microns, preferably between 2 and 3 microns.
[0058] In another embodiment, each of the unglazed silica layers has approximately the same thickness (that is, each layer has the same thickness with a ± 5% margin between the different layers).
[0059] In another embodiment, the unglazed silica layers have approximately the same volume (ie each layer has the same volume with a margin of ± 5% between the different layers). When the interior space of the substrate tube decreases with the increase in the number of layers deposited, the thickness of the layers can increase when the volume remains the same (the reduction in diameter leads to an internal surface
ES 2 646 945 T3 diminished).
[0060] In another embodiment, the total deposited unglazed silica layers have a thickness of between 1 and 1000 microns. Depending on the type of mechanical removal used, there are different preferred ranges for the number of unglazed silica layers. This is explained in more detail below. In this embodiment, the thickness is the thickness of all the unglazed layers together.
In another aspect, the present invention relates to a process in which the precursor for a primary preform is used as a substrate tube for the manufacture of a primary preform by means of a plasma-assisted internal deposition process. This plasma-assisted deposition process preferably comprises the steps of:
a) providing said precursor for a primary preform; Y
b) creating inside said hollow substrate tube a plasma reaction zone having reaction conditions by means of electromagnetic radiation to effect the deposition of vitrified silica layers on the internal surface of said precursor for a primary preform provided in step a).
[0062] In one embodiment, the electromagnetic radiation used is microwaves.
The present invention will be discussed in more detail below.
Definitions used in the present invention
[0064] The following definitions are used in the present description and in the claims to define the subject matter. Other terms not mentioned below have the generally accepted meaning in the technical field. Hollow substrate tube as used in the present description means: a tube, preferably elongated, having an internal cavity. Generally, the interior of such a tube is provided (or lined) with a plurality of layers of glass during the manufacture of a preform. Precursor for a primary preform as used in the present description means: an intermediate product that will lead to a primary preform after one or more additional process steps. Primary preform as used in the present description means: a solid rod (solid preform) that requires to be provided externally with additional glass before becoming a final preform. Final preform as used in the present description means: a solid rod (solid composite preform) that will be used directly to draw optical fibers therefrom. Tube deposited as used in the present description means: a hollow tube that is made up of layers of vitrified silica deposited within a tube of substrate that has been removed. In other words, the substrate tube is no longer present in this deposited tube. Cavity as used in the present description means: the space surrounded by the wall of the substrate tube. Gas supply side or supply side as used in the present description means: a substrate tube side, which is an open end of the substrate tube that is used as an inlet for the gases. The supply side is the side opposite the discharge side. Gas discharge side or discharge side as used in the present description means: one side of the substrate tube, which is an open end of the substrate tube that is used as an outlet for the gases. The discharge side is the side opposite the supply side. Inner surface as used in the present description means: the inner surface or the inner surface of the hollow substrate tube. Glass or glass material as used in the present description means: crystalline or vitreous (vitreous) oxide material - for example silica (SO2) or even quartz - deposited by a vapor phase deposition process. Silica as used in the present description means: any substance in the form of SiOx, whether or not it is stoichiometric, and whether or not it is crystalline or amorphous. Alumina as used in the present description means: any substance in the form of AlyOx, where Al is aluminum and O is oxygen, whether stoichiometric or not, and whether or not it is crystalline or amorphous. "Glass forming gases" as used herein means: reactive gases used during the deposition process to form layers of glass. These glass-forming gases can comprise a precursor for a dopant (eg, O2 and SiCl4 and optionally others). Precursor for a dopant as used in the present description means: a compound or composition that, when introduced into glass, becomes a dopant that has an effect on the refractive index of the glass. Dopant precursors can be, for example, gases that react with one or more compounds in the glass-forming gases to form layers of doped glass when vitrified. During glass deposition, a dopant precursor is introduced into the glass layers. Dopant as used in the present description means: a compound or composition that is present in the glass of the optical fiber and that has an effect on the refractive index of said glass. For example, it may be a reducing agent dopant, namely a refractive index lowering dopant, such as fluorine or boron (for example, it is introduced as a precursor in the form of F2, C2F8 SF6, C4F8 or BCh). For example, it can be a positive dopant, namely a dopant that increases the refractive index, such as germanium (for example, introduced as a precursor in the form of GeCl2 (germanium dichloride) or GeCL (germanium tetrachloride)) . Dopants can be present in the glass in the interstices of the glass (for example, in the case of F) or they can be present as an oxide (for example, in the case of germanium, aluminum, phosphorus or boron). Un vitrified silica is the same as soot as used herein and means: incompletely vitrified (= partially vitrified) silica. It can be undoped or doped. Vitrified silica is the same as glass as used herein and means: a glassy substance produced by the complete vitrification of silica. It can be doped or undoped. Soot deposition as used herein means: the deposition of unglazed silica on the inner walls of the substrate tube. Soot deposition is visually appreciable as a white opaque fine particulate material. Reaction zone as used in the present description means: the zone or axial location in which the
ES 2 646 945 T3 glass forming reaction or deposition. This zone is formed by a plasma and preferably reciprocally moves along the longitudinal length of the substrate tube. Reaction conditions as used in the present invention mean: a set of conditions such as temperature, pressure, electromagnetic radiation that are used to effect the deposition of the silica layers (unglazed or vitrified). Plasma as used in the present description means: an ionized gas consisting of positive ions and free electrons in proportions that result in more or less total electrical charge at very high temperatures. The plasma is induced by electromagnetic radiation, preferably by microwaves. Inversion point as used in the present description means: the point or axial position in the substrate tube where the movement of the applicator oscillates. In other words, back and forth swings back and forth. It is the turning point of the applicator. The axial point is measured in the middle (longitudinal) of the applicator. Near the inversion point as used in the present description means: an axial position in the substrate tube that is close in terms of distance to the inversion point or is in the same position as the inversion point. At the point of inversion as used in the present description means: an axial position in the substrate tube that is in the same position as the point of inversion. Reciprocating as used in the present description means: reciprocating forward and backward movement in a straight line. Phase as used in the present description means: a part of the deposition process in which layers of glass having a specific refractive index value are deposited. The specific value can be constant or exhibit a gradient. For example, for a single step index fiber, core deposition and cladding deposition are each considered as a separate phase. Stroke or pass as used in the present description means: each back and forth movement of the applicator along the length of the substrate tube.
Detailed description of the invention
[0065] The present invention relates, in a first aspect, to a process for manufacturing a precursor for a primary preform for optical fibers by means of a plasma-assisted internal deposition process. During this process, the substrate tube is removed. In a second aspect, the present invention relates to a method for removing a substrate tube from layers of glass deposited on its internal surface by means of a plasma-assisted internal deposition process. In a third aspect, the present invention relates to a process for manufacturing a primary preform for optical fibers by means of a plasma-assisted internal deposition process.
[0066] The solution that the present inventors have found for the problems cited above in the prior art is the elimination of the substrate tube, which allows the use of a substrate tube other than quartz. This solution involves the removal of the substrate tube after the deposition of the silica layer inside said substrate tube. This removal is facilitated by the presence of a layer of soot (unglazed glass) between the internal surface of said substrate tube and the deposited glass layers. This silica soot has a certain adhesion (although limited) to the glass layers to be deposited and has a certain (although limited) adhesion to the substrate tube, which can for example be made of alumina. Therefore, it acts as a barrier between two vitrified parts, firstly the substrate, which is preferably a glass or silica-based substrate tube and, on the other hand, the layers of glass that are deposited. This barrier layer will act as a non-stick layer or intermediate layer that allows the separation of the two layers of vitrified silica on each side. In principle, it can be seen as an intermediate layer between two tubes, on the outside of the substrate tube and on the inside of the deposited tube.
[0067] The adhesion of the soot layer (unglazed silica layer) to the substrate tube should be sufficient on the one hand to allow a layer to form (preferably a continuous layer, and / or preferably a layer having a covering substantially constant of the inner surface of the substrate tube, and / or preferably a layer having an essentially constant thickness along the length of the substrate tube). The adhesion of the soot layer to the substrate tube, on the other hand, should not be too high to allow separation of the substrate tube from the soot layer.
The adhesion of the soot layer to the glass layers to be deposited should, on the one hand, be sufficient to allow the glass layers to form. The adhesion of the soot layer to the glass layers to be deposited, on the other hand, should not be too high to allow separation of the glass layers from the soot layer.
[0069] In the present invention it is possible for the unglazed silica layers to be removed using a liquid, for example water or other aqueous solution. The brittle unglazed silica particles are broken down so that a fine, powder-like material dispersed in the liquid is obtained, which can be removed by removing the liquid.
[0070] The substrate tube used in accordance with the present invention is preferably a non-quartz substrate tube. It is possible to use a tube of quartz substrate, for example of lower purity. The substrate tube must be able to withstand high temperatures that are used in the deposition process. Furthermore, the substrate tube should be transparent to electromagnetic radiation to allow the formation of a plasma within said substrate tube. The internal and external dimension of the substrate tube used in the present invention can be selected according to the requirements of the process equipment and the amount and type of optical fiber to be formed. The substrate tubes may be required to undergo a pretreatment process in order to make them suitable for use in the plasma deposition equipment used in the present invention.
ES 2 646 945 T3
The present method comprises the following steps, which are not all essential for all embodiments. Some of these stages may take place in a different order.
The first step is to provide a hollow glass tube. Said hollow substrate tube may preferably have a supply side and a discharge side. This hollow substrate tube is used for the internal deposition of layers on the internal surface of the same. A gas line (or optionally a main gas line and at least one secondary gas line) are attached to said supply side and preferably a vacuum pump is attached to said discharge side.
In another step, a gas flow is supplied into said hollow substrate tube. This gas flow is preferably introduced through the supply side of said substrate tube. Said gas flow comprises at least one glass-forming gas. For example, oxygen and silicon tetrachloride. Optionally, said gas flow also comprises, during at least a part of the deposition process, at least one precursor for a dopant, such as germanium (for example, in the form of germanium tetra or dichloride) and / or fluorine (for example , in the form of C2F6). First, only oxygen is introduced, later optionally a etching gas, even later glass-forming gases.
[0074] In a later stage, a plasma reaction zone is created inside said hollow substrate tube. The plasma reaction zone does not span the entire length of the substrate tube, but only a portion surrounded by the applicator. In other words, the plasma reaction zone is created in a part of the interior of the hollow substrate tube. Plasma is created by means of electromagnetic radiation. This plasma reaction zone provides the suitable conditions to effect the deposition of layers of vitrified glass or layers of unglazed glass -depending on the conditions- on the internal surface of said hollow substrate tube by allowing the reaction of the formation gases. glass and optionally one or more dopant precursors. In other words, the plasma reaction zone is the three-dimensional space that the plasma occupies within the substrate tube.
The reaction zone preferably reciprocates between two reversal points, each of which is located at or near the ends of the substrate tube. There is an investment point close to the supply side, there is an investment point close to the discharge side. The electromagnetic radiation applicator is present coaxially on the substrate tube. The formed plasma travels back and forth along the longitudinal axis of said hollow substrate tube together with the applicator. The movement oscillates between a reversal point located near the supply side and a reversal point located near the discharge side of said hollow substrate tube. This reciprocity takes place several times (called passes or strokes) and during each pass or stroke a thin layer of vitrified or unglazed glass is deposited. In the case that the deposition process is carried out in several phases, each phase comprises a plurality of strokes, for example between 1000 and 10,000, such as 2000 to 4000 strokes.
[0076] During step ii) of the present process of the invention, a first plasma reaction zone is provided for the deposition of unglazed glass. The first reaction conditions apply. These first reaction conditions are effective for the production of unglazed silica layers, in other words, these conditions are chosen to avoid deposition of vitrified silica. A gas flow of glass-forming gases is present during this stage. In one embodiment, a high pressure (eg,> 50 mbar) is used to prevent vitrification. This is a consequence of the fact that pressure determines the amount of silica formation in the gas phase. When the pressure in the substrate tube is low enough, only a small amount of soot (SiO2 or GeC> 2) will form in the gas phase and most glass-forming gases will react as vitrified silica on the inside diameter of the substrate tube. If the pressure is greater than 50 mbar, there will be a significant amount of soot through the accumulation of silica particles in the gas phase before deposition on the internal diameter of the substrate tube. Soot will adhere to the substrate tube and can be removed later. If the plasma deposition process is carried out in a higher pressure regime (> 30 mbar or even> 60 mbar), the deposition is found to consist of a large part of soot material. [0077] It should be noted that preferably the unglazed silica is supplied over a large part of the inner surface of the substrate tube, such as between the point of inversion near the supply side and the point of inversion near the discharge side. Preferably, the internal surface area to be covered with the vitrified silica layers is also previously covered by unglazed silica layers. This will facilitate subsequent removal of the substrate tube without damaging the vitrified silica layers, i.e. the deposited layers.
[0078] During step iii) of the present process of the invention, a second plasma reaction zone is provided for the deposition of vitrified silica. Therefore, this step involves creating a second plasma reaction zone having second reaction conditions inside said hollow substrate tube that has deposited layers of unglazed glass on its inner surface by means of electromagnetic radiation to effect the Deposition of vitrified silica layers on the crystallized silica layers deposited in a previous stage. The second reaction conditions used during this step to obtain a plasma reaction zone suitable for glass deposition are known in the art.
[0079] At the end of this deposition stage of the process of the present invention, a substrate tube is obtained having the desired number of layers of vitrified silica deposited on its internal surface. At that moment, the deposition process stops. Therefore, the electromagnetic radiation is stopped as well as the flow of gas comprising glass-forming gases.
[0080] In a next step of the present invention, the substrate tube is removed. This will produce
ES 2 646 945 T3 a so-called deposited tube or layers of vitrified silica that have been deposited.
[0081] In an optional step of the present invention, the deposited tube is subjected to a collapse treatment to form a solid rod. However, it can be envisaged that the finished deposited tube is transported to another facility where this collapsing step is carried out. During this collapsing stage, the hollow tube is heated using an external heat source, such as a furnace or burner, to a temperature between 1800 and 2200 degrees C. In several collapsing runs or passes, the hollow tube heats up and collapses on itself to form a solid rod.
[0082] In an optional step of the present invention, the deposited tube or obtained primary preform can be further provided more externally with an additional quantity of glass, for example by an external vapor deposition process or a direct glass deposition process (so-called overcoat) or by using one or more preformed glass tubes that are provided on the outer surface of the primary preform obtained in accordance with the process of the present invention. This process is called sheathing. When you use a solid rod as a starting point, you get a composite preform called a final preform. In the process according to the present invention, this step of externally providing extra glass can be carried out using doped glass. In a preferred embodiment, the overcoating process uses natural or synthetic silica. This can be doped or undoped silica. In one embodiment, fluorine doped silica is used in the overcoating process, for example to obtain an optical fiber having a buried external optical coating.
From the final preform produced in this way, one end of which is heated, optical fibers are obtained by drawing in a drawing tower. The refractive index profile of the consolidated (collapsed) preform corresponds to the refractive index profile of the optical fiber drawn from said preform.
[0084] Substrate tube removal is preferably about mechanical removal. Mechanical removal can be carried out manually or on a machine.
[0085] There are several ways the substrate tube can be removed. In a first aspect, the substrate tube will remain intact after removal. In a second aspect, the substrate tube will not remain intact after removal.
For example, near both longitudinal ends of the substrate tube a circular (radial) cut is made, preferably through the thickness of the substrate tube, optionally extending into the layer of soot. After this radial cut, the substrate tube is, in principle, coaxially present in an unbonded (loose) manner around the deposited glass layers. The soot layer is brittle and by rotating or sliding the loose substrate tube, this soot layer can be broken or undone to provide displacement between the substrate tube and the glass layers. However, it should be noted that this displacement is very limited in nature as the space between the substrate tube and the glass layer is filled with the layer of soot (broken or discarded).
According to the first aspect, one embodiment is as follows. First, radial cuts are made near both longitudinal ends as discussed above. Next, one (or both) ends of the substrate tube are removed (for example, by making a deeper radial cut that completely passes through the substrate tube and the deposited tube) so that the substrate tube can slide over the layer of glass deposited inside it. This allows the substrate tube to be reused for another deposition process. It is preferred that according to this embodiment the total thickness of the unglazed layers (soot layers) is between 200 and 1000 microns. It is preferred that the number of unglazed layers be between 100 and 500. This leaves a sufficient distance between the two coaxial tubes (ie, the outer substrate tube and the deposited inner tube) for removal.
[0088] For the present invention it is possible that the unglazed silica layers are removed using a liquid, for example water or other aqueous solution. When said liquid is introduced into the space between the two coaxial tubes and the tubes move relatively relative to each other, the brittle unglazed silica particles break apart so that a fine, powder-like material dispersed in the liquid is obtained, which can be removed by removing the liquid. After removing the liquid and the particles, a hollow space is obtained between the two coaxial tubes that facilitates the removal of the outer substrate tube.
For the second aspect, in which the substrate tube does not remain intact, several non-limiting embodiments are provided below.
[0090] In another embodiment, the substrate tube may be subjected to one or more longitudinal cuts (preferably two opposed) (eg, by a machine-driven saw blade). These longitudinal cuts (or cut) preferably extend over the entire length of the substrate tube. These cuts (or cuts) are preferably made through the thickness of the substrate tube, optionally extending into the layer of soot. After making these cuts (or cut), two halves (or more parts) of the substrate tube can be removed. This does not allow reuse of the substrate tube.
[0091] In another embodiment, the substrate tube may be chiseled with a hand hammer to form a crack (or more cracks). These cracks can progress in a longitudinal direction. This will break the substrate tube that is removed into a plurality of parts. This prevents reuse of the substrate tube.
[0092] In another embodiment, the substrate tube is provided with one or more longitudinal or helical grooves made with a diamond glass work blade, followed by rupture of the substrate tube. This could be done either by machine or by hand. This does not allow reuse of the substrate tube.
[0093] For these embodiments of the second aspect, it is not necessary to have a certain thickness of silica
ES 2 646 945 T3 unglazed to allow sufficient separation between the two tubes. To reduce manufacturing time and cost, in this case, the total thickness of the unglazed layers is preferably between 1 and 100 microns, more preferably at most 40 microns, even more preferably at most 20 microns. The number of unglazed silica layers is preferably between 1 and 50, more preferably at most 20, even more preferably at most 10.
[0094] In a further aspect for these embodiments of the second aspect, the ends of the substrate tube (joined ends) can be held in place. This allows easy transfer of the deposited tube (after removal of the substrate tube) to a next stage in the process, for example a collapsing apparatus or a plasma deposition apparatus. In this case, the step of radial cutting close to both longitudinal ends can be carried out as a first step in removing the substrate tube. [0095] In another aspect, the present invention relates to a process in which the precursor for a primary preform is used as a substrate tube for the manufacture of a primary preform by means of a plasma-assisted internal deposition process. This plasma-assisted deposition process preferably comprises the steps of:
a) providing said precursor for a primary preform; Y
b) creating inside said hollow substrate tube a plasma reaction zone having reaction conditions by means of electromagnetic radiation to effect the deposition of vitrified silica layers on the internal surface of said precursor for a primary preform provided in step a).
The precursor for a primary preform used in step a) is the precursor as obtained in a first aspect of the present invention.
[0097] It should be noted that the plasma reaction zone and the reaction conditions of step b) are similar or the same as the second plasma reaction zone and the second reaction conditions described above. It is possible that after step b) a collapsing step is carried out as described above for other aspects. All of the embodiments and information described above regarding the plasma deposition process are also applicable to this embodiment.
[0098] The present invention does not require significant changes in the configuration of the apparatus or instruments that are already in use. Therefore, the solution to the problem presented in the present invention is easy and cost-effective to implement.
The present invention will now be explained on the basis of an example, in connection with which it should be noted, however, that the present invention is in no way limited to this example.
Example
[0100] A low-grade silica tube provided at both ends with a welded glass rod (handle) is placed on a PCVD lathe surrounded by a furnace. The oven is brought up to a temperature of 1100 ° C while oxygen passes through the substrate tube at a pressure of 15 millibars. The speed of the resonator is 20 meters per minute. A plasma is induced and the pressure increases to 60 millibars. Approximately 20 layers of undoped and unglazed silica are deposited in a 2 minute period. The pressure is subsequently reduced to approximately 14 millibar and approximately 160 layers of vitrified silica are deposited in approximately 12 minutes.
[0101] When the entire process is finished, the tube is taken out of the PCVD lathe to cool it in ambient air (no forced cooling is applied). When the tube is at room temperature (23 ° C), a saw cut is made near the gas supply side (50 millimeters from the end of the tube) and near the discharge side (100 millimeters from the end of the tube) . The substrate tube is then removed from the deposited tube using a chisel and hammer. The two joined ends remain in position. The deposited tube is provided to a collapsing apparatus and is collapsed to provide a solid core rod.
[0102] In this way, one or more objectives of the present invention mentioned above are achieved. Further embodiments of the present invention are cited in the appended claims.
Contents3
21 members in 11 offices
Priority claims9
| Document | Office | Kind | Date |
|---|---|---|---|
| 2011075 | Netherlands (Kingdom of the) | A | |
| 2011075 | Netherlands (Kingdom of the) | A | |
| 2011075 | Netherlands (Kingdom of the) | – | |
| 2014050357 | Netherlands (Kingdom of the) | W | |
| 2014050357 | Netherlands (Kingdom of the) | W | |
| 2011075 | – | – | – |
| NL20132011075 | – | – | – |
| PCTNL2014050357 | – | – | – |
| WO2014NL50357 | – | – | – |
Members21
| Document | Office | Kind | |
|---|---|---|---|
| NL2011075C2 | Netherlands (Kingdom of the) | C2 | |
| WO2015002530A1 | World Intellectual Property Organization (WIPO) | A1 | |
| CN105358496A | China | A | |
| KR20160025526A | Republic of Korea | A | |
| EP3016915A1 | European Patent Office (EPO) | A1 | |
| US2016152509A1 | United States of America | A1 | |
| US2016186316A1 | United States of America | A1 | |
| JP2016527169A | Japan | A | |
| BR112015032407A2 | Brazil | A2 | |
| RU2016102888A | Russian Federation | A | |
| EP3016915B1 | European Patent Office (EPO) | B1 | |
| JP6214766B2 | Japan | B2 | |
| DK3016915T3 | Denmark | T3 | |
| US9816178B2 | United States of America | B2 | |
| US9816179B2 | United States of America | B2 | |
| ES2646945T3This record | Spain | T3 | |
| RU2016102888A3 | Russian Federation | A3 | |
| RU2652215C2 | Russian Federation | C2 | |
| CN105358496B | China | B | |
| KR102235333B1 | Republic of Korea | B1 | |
| BR112015032407B1 | Brazil | B1 |
Numbers
- Publication
- 2646945
- Publication, DOCDB
- 2646945
- Publication, EPODOC
- ES2646945T
- Application
- 14732648
- Application, DOCDB
- 14732648
- Application, EPODOC
- ES20140732648T
Titles2
- Spanish
- Proceso para deposición asistida por plasma con eliminación del tubo de substrato
- English
- Process for plasma-assisted deposition with removal of the substrate tube
Classification
- CPC, 4
- C03B37/0183
- C03B37/018
- C23C16/01
- C23C16/402
- IPC, 3
- C03B37 018
- C23C16 01
- C23C16 40