US20120328876A1 - Method for producing ceramic fibers of a composition in the sic range and for producing sic fibers - Google Patents
Method for producing ceramic fibers of a composition in the sic range and for producing sic fibers Download PDFInfo
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- US20120328876A1 US20120328876A1 US13/539,662 US201213539662A US2012328876A1 US 20120328876 A1 US20120328876 A1 US 20120328876A1 US 201213539662 A US201213539662 A US 201213539662A US 2012328876 A1 US2012328876 A1 US 2012328876A1
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/04—Dry spinning methods
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
- C04B35/565—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide
- C04B35/571—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide obtained from Si-containing polymer precursors or organosilicon monomers
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- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/62227—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres
- C04B35/62272—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres based on non-oxide ceramics
- C04B35/62277—Fibres based on carbides
- C04B35/62281—Fibres based on carbides based on silicon carbide
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
- C08G77/50—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages
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- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
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- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
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- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/48—Organic compounds becoming part of a ceramic after heat treatment, e.g. carbonising phenol resins
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Definitions
- the invention relates to a method for the production of silicon carbide fibers from a polysilane-polycarbosilane copolymer solution.
- preferred methylchlorodisilanes that are used are those that are formed as the high boiling point fraction in the Müller-Rochow synthesis; since they are therefore by-products, they constitute inexpensive raw materials. They usually consist of a mixture of 1,1,2,2-tetrachlorodimethyldisilane and 1,1,2-trichlorotrimethyldisilane with less than 10% molar of other ingredients.
- the crude polysilane is produced by disproportionation of the disilane mixture using an organic nitrogen compound as a Lewis base as the homogeneous catalyst, preferably at a raised temperature, with the monosilane mixture that forms during the reaction as the cleavage product being continuously distilled off.
- the raw polysilane is rendered infusible by increasing the average molecular weight and then is converted, via a rearrangement reaction, into a polysilane-polycarbosilane copolymer (hereinafter abbreviated to “PPC”).
- PPC polysilane-polycarbosilane copolymer
- fibers can be spun from a solution of this type that can be transformed into SiC fibers by a pyrolysis step.
- the solutions must have a 30% to 95% by weight polysilane-polycarbosilane copolymer content in order to be spinnable and thus to be able to be used as a spin dope.
- solutions with substantially lower PPC contents for example 20% by weight, can only be turned into ceramic matrixes by employing a liquid phase infiltration method.
- the known method for the production of SiC fibers has the disadvantage in that with the PPC concentrations employed, relatively large capillary diameters of 75 to 300 ⁇ m are required in the spin nozzles used for spinning in order to be able to force the relatively viscous spin dope with a 30% to 95% by weight PPC content through.
- the green fibers obtained in the spinning duct immediately after leaving the spin nozzles have a relatively large diameter, also approximately between 75 and 300 ⁇ m.
- fibers with a final diameter after pyrolysis of substantially under 40 ⁇ m, preferably approximately 10 ⁇ m, are desired.
- the filaments coming out of the spin nozzles have to be stretched by very high draw rates of up to 500 m/min.
- the known method for the production of SiC fibers also suffers from the disadvantage that trouble-free spinning is not possible. Breaks occur frequently at the nozzles so that at least for a fraction of the spin nozzles used, a joining has to be made, which either breaks a complete fiber bundle at that location or results in extremely severe inhomogeneities within the bundle. Thus, the known method cannot be used to produce a fiber bundle of homogeneous quality; in particular, the individual fibers do not all have the same diameter.
- the SiC fibers produced using the method described in DE 10 2004 042 531 A1 have a kidney-shaped cross section.
- a diameter of 30 ⁇ m is relatively large.
- the aim of the invention is to overcome the disadvantages mentioned above, in particular to provide a method for the production of SiC fibers, which means that the green fibers can be spun in a circumspect manner, so that undamaged or only slightly damaged SiC fibers can be obtained following transformation into ceramic fibers by pyrolysis; moreover, they have a near-circular cross section and also a high Y modulus and high strength.
- low viscosity PPC solutions with PPC contents of below 25% by weight which previously were used only in liquid phase infiltration, can surprisingly be spun if they are extruded through nozzles with capillary diameters of 20 to 70 m, in particular 30 to 60 ⁇ m, more particularly in the range 40 to 50 ⁇ m.
- This type of small nozzle capillary diameter means that, even when the spin dope leaves the nozzles, the green fibers formed have a smaller diameter that is already almost that of the target diameter of the green fibers. In this manner, the fibers do not have to be stretched much more in order to reach the desired diameter. This conserves the green fibers and results in less damage and fewer surface defects.
- filaments can even form from the low viscosity spin dope with an extremely high solvent fraction. This is presumably only possible because the spin dope is extruded through spin nozzles with a very small nozzle capillary diameter and the filaments coming out of the spin nozzles, which have a correspondingly small filament diameter, have a high surface to volume ratio. Therefore the solvent evaporates quickly and the spin dope that is now in the form of fibers gels rapidly, and thus becomes firm enough for it not to lose its fibrous shape. Despite the small nozzle capillary diameter, and because of the low viscosity, very high throughputs are obtained so that the fibers that are formed have to be drawn at high rates just to “catch” the volume of material that is being discharged.
- the spinning process is trouble-free and without fiber breakage using the method of the invention.
- gas inclusions in the low viscosity spin dope can escape upwards more easily than in higher viscosity spin dopes so that the high solvent content prevents the fibers from breaking.
- the small spin nozzle diameter also means that the spin dope cannot flow out of the nozzles unhindered, but have to be put under a certain (albeit very low) pressure.
- the spin dope is stretched while in free fall. Then the solvent evaporates; this can be encouraged by appropriate adjustment of the spinning duct and spin dope parameters. In this manner, sufficient solvent is removed from the fiber to result in gelling, i.e. solidification of the fiber to an extent such that it can no longer run away.
- a second stretching zone drawing at a certain winding rate can further stretch the gelled fibers.
- the fibers obtained surprisingly have a generally circular cross section. It is known that prior art fibers with a kidney-shaped cross section are obtained because initially, only the sheath area of the green fibers leaving the nozzles solidifies, while the remaining core is still liquid. In the context of the invention, it has been observed that too much stretching when drawing means that the forces on the green fibers in the longitudinal direction deform the fibers. Since the core is still liquid inside the solidified sheath zone, on stretching, here and there the forces cause the fibers to collapse so that the cross section becomes kidney-shaped. This problem is surprisingly overcome in the method of the invention because the green fibers exiting the nozzles are already thin. Because of this, severe stretching using the damaging forces described is not necessary and a fiber retains the round cross section it possesses when it exits the nozzle right up to when it is wound, for example onto take-up rolls.
- SiC fibers as used in the present invention means fibers with a chemical composition that is in the silicon carbide range, but wherein the atomic ratio of silicon to carbon is not necessarily exactly 1:1 but may deviate from this to a higher Si content or a higher C content, as well as other elements or compounds as impurities.
- spinning is carried out at a draw rate in the range 50 m/min to 1000 m/min, in particular in the range 100 to 750 m/min, preferably in the range 200 to 500 m/min.
- draw rate in the range 50 m/min to 1000 m/min, in particular in the range 100 to 750 m/min, preferably in the range 200 to 500 m/min.
- the spin dope has a viscosity in the range 0.1 to 6 Pas, in particular in the range 0.5 to 4 Pas at temperatures in the range 20° C. to 80° C.
- the spin dope preferably flows from the spin nozzles even at pressures from 1 bar, such as in the range 1 to 40 bar. In this manner, there is very little danger that gas under high pressure will be dissolved or included in the low viscosity spin dope and result in breakage at the spin nozzle.
- spinning is carried out at a shear rate in the range 10,000 s ⁇ 1 to 60,000 s ⁇ 1 , in particular in the range 20,000 to 40,000 s ⁇ 1 .
- the spinning duct temperature is adjusted such that after the spin dope exits the spin nozzles, the solvent evaporates even faster from the green fibers being formed.
- Temperatures in the range 30° C. to 160° C., in particular in the range 50° C. to 100° C., particularly preferably in the range 60° C. to 80° C. are preferred. These should be optimized for each individual case as a function of the vapor pressure curve of the solvent or solvents employed.
- a high partial counter pressure of the solvent which is also present in the PPC solution and is usual in the prior art, is not set up in the spinning duct; in contrast, the solvent that comes out of the green fibers in the course of formation is removed more rapidly by flushing the spinning duct with a flushing gas that is free of solvent.
- a flushing gas such as nitrogen (N 2 ) or argon (Ar).
- rapid evaporation of the solvent can be encouraged by not injecting the inert gas used during spinning as a counter-current, but by injecting it in the same direction as the fibers, from top to bottom. This prevents solvent that is evaporating from the fiber from being applied again to the fibers further up in the spinning duct and being taken up by them or at least making evaporation of the solvent from the fibers more difficult by building up a high partial pressure.
- Preferred solvents for the PPC composition are: a saturated hydrocarbon selected from the group formed by n-pentane, n-hexane, cyclohexane, n-heptane, n-octane, an aromatic hydrocarbon selected from the group formed by benzene, toluene, o-xylene, syn-mesitylene, a chlorinated hydrocarbon selected from the group formed by methylene chloride, chloroform, carbon tetrachloride, 1,1,1-trichloroethane, chlorobenzene or an ether selected from the group formed by diethyl ether, diisopropyl ether, tetrahydrofuran, 1,4-dioxane or a mixture of two or more of these solvents.
- a saturated hydrocarbon selected from the group formed by n-pentane, n-hexane, cyclohexane, n-heptane, n-oct
- the temperatures in the spinning duct are preferably in the range 50° C. to 100° C., in particular in the range 60° C. to 80° C.; the temperature of the PPC solution in the spinning vessel is preferably in the range 20° C. to 40° C., in particular in the range 25° C. to 35° C.
- the preferred temperatures of the PPC solution and the spinning duct are adjusted accordingly, in particular as a function of the vapor pressure curves for the relevant solvent; the temperatures selected are those that provide similar vapor pressures to those obtained for toluene in the cited temperature ranges.
- the PPC solution may be supplemented with an organic polymer as a spinning aid.
- This spinning aid is preferably selected from the group consisting of polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyacrylonitrile and poly(4-vinyl pyridine).
- the quantity of spinning aid in the solution with respect to the substitutive fraction of the PPC preferably amounts to in the range 0.5% to 10% by weight.
- PPC solutions can be spun without spinning aid. This has the advantage that no additional substances are present in the fiber for pyrolysis that do not contribute to the target stoichiometry of the SiC fibers and/or that reduce the density of the pyrolyzed fibers.
- the green fibers are preferably pyrolyzed in an inert atmosphere such as nitrogen and/or argon, or in a reducing atmosphere, in particular in a gas mixture consisting of argon and hydrogen or nitrogen and carbon monoxide or similar combinations formed from at least one carrier gas and at least one reducing gas.
- the pyrolysis is preferably carried out at temperatures over 200° C., in particular over 300° C., in particular in the range 700° C. to 1,700° C., more particularly in the range 900° C. to 1,300° C.
- the pyrolyzed fibers can advantageously be sintered at temperatures in the range 1,000° C. to 1,500° C. when, for example, a lower porosity or larger grain size is desired.
- Fibers in the SiC zone have an oxygen content of less than 1% by weight, in particular in the range 0.3% to 0.9% by weight, an Y modulus of more than 130 GPa, in particular more than 150 GPa and a tensile strength of more than 1.5 GPa, in particular 2 GPa, more particularly more than 3.1 GPa. These particularly good mechanical properties are surprisingly attainable by means of the method of the invention.
- SiC fibers produced in accordance with the method of the invention have a diameter in the range 5 to 50 ⁇ m, in particular in the range 6 to 40 ⁇ m, preferably in the range 7 to 20 ⁇ m.
- the Si content of the SiC fibers is advantageously in the range 30% to 70% atomic; the C content is in the range 30% to 70% atomic; particularly preferably, each is in the range 40% to 60% by weight, in order to approximate to the stoichiometric ratio as closely as possible; advantageously, the C is in slight excess.
- green fiber bundles and the pyrolyzed SiC fiber bundles formed therefrom are produced with a uniform number of fibers. Because the problem of constantly having to join on new individual fibers has been overcome, the bundles are also free of occasional increased diameters or bulges.
- the aim of the invention is also achieved by a SiC fiber bundle formed from 10 to 50,000, in particular 100 to 10,000, in particular 200 to 2,000 individual SiC fibers that are highly regular.
- the term “highly regular” as used in the context of the invention in particular means that of the individual fibers, fewer than 20% have a diameter that deviates from the mean fiber diameter of the bundle, for example in the range 5 to 50 ⁇ m, by more than 30%.
- a high regularity of this type means that the overall bundle has very good mechanical properties and very good processability.
- a polysilane-polycarbosilane copolymer was prepared in accordance with DE 10 2004 042 531 A1, starting from a methylchlorodisilane mixture from the Müller-Rochow process.
- the polysilane-polycarbosilane copolymer was converted into a solution containing less than 25% by weight of PPC using toluene as the solvent, for example.
- the PPC content was 20% by weight.
- the polysilane-polycarbosilane copolymer solution was used as the spin dope and was placed in a pressure vessel of a spinning apparatus under nitrogen as the inert gas and heated to 40° C. to 70° C.
- the spin dope was fed by a spinning pump to a spinneret which had 500 individual spin nozzles with a nozzle capillary diameter of 40 ⁇ m in this example.
- the spin dope was extruded through the spin nozzles and drawn using a godet roll (galette) through a spinning duct. The draw rate varied between 50 and 500 m/min. At all spinning speeds, the spinning process was very regular and there were no breaks in the green fibers at the spinneret.
- a 1000 m long fiber bundle was spun at a speed of 200 m/min.
- a plurality of 50 cm long sections taken from the green fiber bundle at regular distances along its length were taken and heated, under nitrogen as the inert gas atmosphere at a heating rate of 250 K/min, to 1,300° C. and pyrolyzed for 1 min at this temperature.
- the whole fiber bundle could have been pyrolyzed in a single continuous process step. If densification was required, a sintering step could have been carried out subsequently at up to 1,500° C. for 1 min, for example.
- the individual fibers of the SiC fiber bundle obtained were highly regular, both between themselves and also along the longitudinal direction. Fewer than 5% of the fibers in the fiber bundle deviated by more than 10% from the mean value of the fiber diameter, determined to be 12 ⁇ m.
- the invention is not limited to the combination of the features mentioned, but encompasses all conceivable combinations of the described features, insofar as they do not contradict the ambit of the invention.
- the invention also encompasses spinning spin dopes with a lower solvent content wherein, however, an appropriately low viscosity is obtained by measures other than the solvent content, such as a lower molecular mass, viscosity-reducing additives or the like.
- an appropriately low viscosity is obtained by measures other than the solvent content, such as a lower molecular mass, viscosity-reducing additives or the like.
- viscosities are obtained that correspond to those of the high solvent content solutions of the invention.
- cooperation with a small nozzle capillary diameter results in a trouble-free spinning process with a regular fiber bundle, wherein the viewing window fibers obtained have a high Y modulus and a high tensile strength because of the alignment of the polysilane-polycarbosilane copolymers.
- the invention also encompasses spinning other spin dopes containing polysilane and/or polycarbosilane with a high solvent content and/or low viscosity and small nozzle capillary diameters and thus to obtain a trouble-free spinning process and to produce a regular SiC fiber bundle that contains high modulus ceramic fibers with a high tensile strength.
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US14/699,089 US9885126B2 (en) | 2009-12-30 | 2015-04-29 | Method for producing ceramic fibers of a composition in the SiC range and for producing SiC fibers |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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DE102009055429A DE102009055429A1 (de) | 2009-12-30 | 2009-12-30 | Verfahren zur Herstellung von Keramikfasern mit einer Zusammensetzung im Bereich SiC und SiC-Fasern |
DE102009055429.7 | 2009-12-30 | ||
PCT/EP2010/070430 WO2011080162A1 (de) | 2009-12-30 | 2010-12-21 | VERFAHREN ZUR HERSTELLUNG VON KERAMIKFASERN MIT EINER ZUSAMMENSETZUNG IM BEREICH SiC UND SiC-FASERN |
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PCT/EP2010/070430 Continuation WO2011080162A1 (de) | 2009-12-30 | 2010-12-21 | VERFAHREN ZUR HERSTELLUNG VON KERAMIKFASERN MIT EINER ZUSAMMENSETZUNG IM BEREICH SiC UND SiC-FASERN |
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US20120328876A1 true US20120328876A1 (en) | 2012-12-27 |
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US13/539,662 Abandoned US20120328876A1 (en) | 2009-12-30 | 2012-07-02 | Method for producing ceramic fibers of a composition in the sic range and for producing sic fibers |
US14/699,089 Active 2031-09-01 US9885126B2 (en) | 2009-12-30 | 2015-04-29 | Method for producing ceramic fibers of a composition in the SiC range and for producing SiC fibers |
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US (2) | US20120328876A1 (de) |
EP (1) | EP2519481B1 (de) |
DE (1) | DE102009055429A1 (de) |
WO (1) | WO2011080162A1 (de) |
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CN113026126A (zh) * | 2021-03-10 | 2021-06-25 | 厦门大学 | 一种聚碳硅烷干法纺丝方法 |
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EP3953416B1 (de) * | 2019-04-08 | 2022-10-26 | Merck Patent GmbH | BLOCKCOPOLYMER ENTHALTENDE ZUSAMMENSETZUNG UND
VERFAHREN ZUR HERSTELLUNG EINES KIESELSÄUREFILMS DAMIT |
CN110079896B (zh) * | 2019-04-17 | 2021-04-30 | 中国人民解放军国防科技大学 | 一种碳化硅纳米纤维束及其制备方法 |
CN110983797B (zh) * | 2019-12-13 | 2022-04-26 | 武汉纺织大学 | 一种热隐形柔性材料及其制备方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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US5162269A (en) * | 1990-01-16 | 1992-11-10 | Dow Corning Corporation | Polycrystalline silicon carbide fibers |
US5171722A (en) * | 1991-10-09 | 1992-12-15 | University Of Florida | SiC fibers having low oxygen content and methods of preparation |
US5354527A (en) * | 1992-02-21 | 1994-10-11 | The Carborundum Company | Process for making silicon carbide ceramic fibers |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4010233A (en) * | 1970-11-06 | 1977-03-01 | Bayer Aktiengesellschaft | Production of inorganic fibers |
DE2243527A1 (de) * | 1972-09-05 | 1974-04-18 | Bayer Ag | Formkoerper aus homogenen mischungen von siliciumcarbid und siliciumnitrid und verfahren zu ihrer herstellung |
US5242870A (en) * | 1991-10-09 | 1993-09-07 | University Of Florida | SIC fibers having low oxygen content and methods of preparation |
US5792416A (en) * | 1996-05-17 | 1998-08-11 | University Of Florida | Preparation of boron-doped silicon carbide fibers |
TW459075B (en) * | 1996-05-24 | 2001-10-11 | Toray Ind Co Ltd | Carbon fiber, acrylic fiber and preparation thereof |
GB9824621D0 (en) * | 1998-11-11 | 1999-01-06 | Univ Strathclyde | Super selective hollow fibre membranes |
DE102004042531A1 (de) | 2004-05-03 | 2005-12-15 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Polysilan-Polycarbosilan-Copolymer-Lösungen und daraus hergestellte sauerstoffarme keramische Formkörper mit Zusammensetzungen nahe SiC |
DE102008064372A1 (de) * | 2008-12-22 | 2010-06-24 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Polysilan-Polycarbosilane mit reduziertem Chlorgehalt auf Basis von Methylchlorpolysilanen sowie daraus hergestellte Spinnmassen und keramische Formkörper |
DE102009056371A1 (de) * | 2009-11-30 | 2011-07-14 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V., 80686 | Polysilan-Polycarbonsilane mit reduziertem Kohlenstoffgehalt auf Basis von Methylchlorpolysilanen sowie daraus hergestellte Keramiken |
-
2009
- 2009-12-30 DE DE102009055429A patent/DE102009055429A1/de not_active Ceased
-
2010
- 2010-12-21 EP EP10798324.9A patent/EP2519481B1/de active Active
- 2010-12-21 WO PCT/EP2010/070430 patent/WO2011080162A1/de active Application Filing
-
2012
- 2012-07-02 US US13/539,662 patent/US20120328876A1/en not_active Abandoned
-
2015
- 2015-04-29 US US14/699,089 patent/US9885126B2/en active Active
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US5162269A (en) * | 1990-01-16 | 1992-11-10 | Dow Corning Corporation | Polycrystalline silicon carbide fibers |
US5171722A (en) * | 1991-10-09 | 1992-12-15 | University Of Florida | SiC fibers having low oxygen content and methods of preparation |
US5354527A (en) * | 1992-02-21 | 1994-10-11 | The Carborundum Company | Process for making silicon carbide ceramic fibers |
Non-Patent Citations (1)
Title |
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http://www.schenectady.k12.ny.us/users/pattersont/Computer%20Prog%20Website/ConversionTable/html. 2014, pgs. 1-2. * |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113026126A (zh) * | 2021-03-10 | 2021-06-25 | 厦门大学 | 一种聚碳硅烷干法纺丝方法 |
Also Published As
Publication number | Publication date |
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WO2011080162A1 (de) | 2011-07-07 |
US9885126B2 (en) | 2018-02-06 |
DE102009055429A1 (de) | 2011-07-07 |
US20150240384A1 (en) | 2015-08-27 |
EP2519481A1 (de) | 2012-11-07 |
EP2519481B1 (de) | 2016-04-20 |
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