EP1268895B1 - Carbonisation de materiaux fibreux cellulosiques en presence d'un compose organosilicie - Google Patents
Carbonisation de materiaux fibreux cellulosiques en presence d'un compose organosilicie Download PDFInfo
- Publication number
- EP1268895B1 EP1268895B1 EP00985406A EP00985406A EP1268895B1 EP 1268895 B1 EP1268895 B1 EP 1268895B1 EP 00985406 A EP00985406 A EP 00985406A EP 00985406 A EP00985406 A EP 00985406A EP 1268895 B1 EP1268895 B1 EP 1268895B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- carbonization
- cellulosic fibrous
- fibrous materials
- organosilicon compound
- carried out
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
- D01F11/10—Chemical after-treatment of artificial filaments or the like during manufacture of carbon
- D01F11/14—Chemical after-treatment of artificial filaments or the like during manufacture of carbon with organic compounds, e.g. macromolecular compounds
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- 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
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/16—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from products of vegetable origin or derivatives thereof, e.g. from cellulose acetate
Definitions
- the subject of the present invention is a process for carbonizing cellulosic fibrous materials, in the presence of at least one organosilicon compound; this, to obtain fibrous carbon materials. Said carbonization can be carried out both continuously and discontinuously.
- the carbon fibrous materials obtained can in turn be heat treated (especially graphitized) to generate fibers having the desired properties.
- Carbon fibers with a cellulose precursor were the first carbon fibers manufactured in the world. Starting from such cellulosic precursors, Edison, in the late 19 th century, obtained filaments for his incandescent lamps (US Patent 223,898).
- Polyacrylonitrile has however proven for a long time a more suitable precursor for obtaining high-strength and high-modulus carbon fibers, more particularly intended for reinforcements of composite materials.
- ex-viscose carbon fibers have been used since 1955 in the manufacture of carbon / phenolic resin composites, used as thermal protection for propellants. These fibers, low modulus, have a restricted thermal conductivity.
- the manufacture of these fibers requires a special rayon type precursor: a rayon with a disoriented crystalline texture (R. BACON, Carbon Fibers from Rayon Precursors, in Chemistry and Physics of Carbon, 1973, Vol. 2, Marcel Dekker, New-York and P. OLRY, 14 th Biennal Conference on Carbon, 1979).
- Said organosilicon product has been described therein as an oligomer chosen from polydimethylphenylallylsilanes, polysiloxanes, polymethylsiloxanes, polysilazanes and polyaluminoorganosiloxanes. In fact, its exact nature is not really specified.
- the originality of the present invention lies in the selection of specific organosilicon compounds - carbonization additives for cellulosic fibrous materials - which are particularly effective.
- Said compounds have been found to be very effective in improving the properties of the carbon fibers obtained after carbonization, this with any type of charred cellulosic materials (rayon, fibrans, in particular commercial); and, that said carbonization is carried out continuously or discontinuously.
- the intervention of said compounds constitutes an undeniable advantage for the implementation of batch and continuous carbonizations, it proves to be essential for the continuous carbonization of certain substrates (it makes said continuous carbonization of said substrates possible. substrates).
- the present invention therefore relates to the use of a particular family of organosilicon compounds in said context.
- the present invention in fact relates to a process for obtaining fibrous carbon materials by carbonization implemented continuously or batchwise, in the presence of at least one organosilicon compound, of cellulosic fibrous materials.
- said organosilicon compound is chosen from the family of polyhydrosiloxanes, cyclic, linear or branched, substituted by methyl and / or phenyl groups, the number average molecular mass of which is between 250 and 10,000, advantageously between 2,500 and 5,000.
- This reinforcement with the additives of the invention, is of remarkable intensity. It makes it possible to counter shrinkage during carbonization and even to stretch the fibers (up to 50%) without breaking them, which ensures an orientation of the texture of said fibers and a reduction or rearrangement of the internal pores. It made it possible to obtain, with any type of cellulose (celluloses with solvent, spokes for tires in particular), filaments which have resistances of the order of 1,500 to 2,000 MPa and modules of the order of 70 to 110 GPa.
- Polyhydrosiloxanes of said family are currently available on the market. Some are sold in particular by the company Rhodia Silicones.
- polyhydrosiloxanes advantageously intervene prior to carbonization; the cellulosic fibrous materials being previously impregnated with these.
- said polyhydrosiloxanes are generally used in solution in a solvent, such as perchlorethylene. Such a solvent can easily be removed before carbonization.
- said polyhydrosiloxanes, selected according to the invention intervene, of course, in an effective amount, generally at a rate of 1 to 10% by weight, relative to the weight of cellulosic materials. It is advisable to put enough to observe the expected effect but not too much because then one can observe an undesirable bonding effect. Those skilled in the art are able to optimize the amount of intervention of the organosilicon compounds, the use of which is recommended in the context of the process of the invention.
- organosilicon compounds could be further enhanced by the joint intervention of a mineral additive.
- the cellulosic fibrous materials are thus also impregnated, before their carbonization, with at least one mineral additive, acid or Lewis base.
- Said mineral additive can in particular be chosen from halides, sulphates and phosphates of ammonium, sodium, urea and their mixtures.
- the additives of the invention are advantageously used, both in carbonization processes used batchwise and in carbonization processes used continuously. We have seen that they made possible the implementation of certain carbonizations continuously (carbonizations that it was only possible to implement, according to the prior art, discontinuously).
- the method of the invention is thus implemented continuously.
- the cellulosic fibrous material may in particular be in the form of threads or textile surfaces (fabrics, knits, felts, nonwovens, unidirectional sheets, unidirectional ribbons, etc.).
- Said cellulosic fibrous material may in particular consist of any type of rayon and fibranne.
- the process of the invention is, in this, particularly interesting: it leads, implemented with products available on the market, of wide distribution, to fibrous carbon materials, of high quality. According to the prior art, such high quality materials could only be obtained from cellulosic fibrous materials of very specific types.
- This pyrolysis carried out batchwise in the context of the example, may well be carried out continuously.
- the carbon filaments extracted from the carbonized wire have a breaking strength of 1,125 MPa and a module of 40 GPa, for a diameter of 5.8 ⁇ m.
- the carbonization shrinkage is 40% along the axis of the fibers.
- the carbonization yield is 15.6%.
- a cellulose yarn identical to that of Example 1 is desensed with perchlorethylene, then impregnated with 2.5% by weight of a polyhydromethylsiloxane resin sold by the company Rhodia Silicones (under the reference: RHODORSIL RTV 141 B) by soaking in a solution at 3% by weight of the product in perchlorethylene.
- RHODORSIL RTV 141 B a polyhydromethylsiloxane resin sold by the company Rhodia Silicones
- the carbon filaments extracted from the wire have a breaking strength of 1,100 MPa, a module of 40 GPa, a diameter of 5.7 ⁇ m.
- the carbonization shrinkage is 40% along the axis of the fibers.
- the carbonization yield is 15.2%.
- a cellulose yarn identical to that of Example 1 is desensed and then impregnated with the organosilicon additive as in Example 1. It is then also impregnated with 8% by weight of NH 4 Cl by passage through an aqueous solution with 13% by weight of said NH 4 Cl.
- the wire is dried at 100 ° C for 30 min and the excess NH 4 Cl is removed by rinsing for a few seconds with distilled water.
- Said wire is dried at 100 ° C for 1 hour then undergoes pyrolysis up to 1200 ° C as in Example 1.
- the tensile strength of the carbon filaments extracted from said carbonized wire is 1,200 MPa and their modulus of 45 GPa, for a diameter of 8.3 ⁇ m.
- the shrinkage during carbonization is 32.3%.
- the carbonization yield is 30%.
- a cellulose yarn identical to that of Example 1 is desensitized with perchlorethylene and then, without impregnation with the polyhydrosiloxane additive, it is pyrolyzed according to the thermal profile indicated in said Example 1.
- the breaking strength of the carbon filaments extracted from the wires obtained is only 660 MPa, their modulus is 38 GPa.
- the diameter of said filaments is 5.8 ⁇ m.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Inorganic Fibers (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Silicon Polymers (AREA)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9915327A FR2801906B1 (fr) | 1999-12-06 | 1999-12-06 | Carbonisation de materiaux fibreux cellulosiques en presence d'un compose organosilicie |
FR9915327 | 1999-12-06 | ||
PCT/FR2000/003388 WO2001042541A2 (fr) | 1999-12-06 | 2000-12-05 | Carbonisation de materiaux fibreux cellulosiques en presence d'un compose organosilicie |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1268895A2 EP1268895A2 (fr) | 2003-01-02 |
EP1268895B1 true EP1268895B1 (fr) | 2004-04-28 |
Family
ID=9552913
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP00985406A Expired - Lifetime EP1268895B1 (fr) | 1999-12-06 | 2000-12-05 | Carbonisation de materiaux fibreux cellulosiques en presence d'un compose organosilicie |
Country Status (12)
Country | Link |
---|---|
US (1) | US7175879B2 (ru) |
EP (1) | EP1268895B1 (ru) |
JP (1) | JP4808351B2 (ru) |
AT (1) | ATE265561T1 (ru) |
AU (1) | AU2183301A (ru) |
BR (1) | BR0016123B1 (ru) |
DE (1) | DE60010347T2 (ru) |
FR (1) | FR2801906B1 (ru) |
MX (1) | MXPA02005625A (ru) |
RU (1) | RU2258773C2 (ru) |
UA (1) | UA72289C2 (ru) |
WO (1) | WO2001042541A2 (ru) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ATE361383T1 (de) * | 2004-12-07 | 2007-05-15 | Snecma Propulsion Solide | Verfahren zur herstellung von garnen oder faserblättern aus kohlenstoff ausgehend von einem cellulosematerial |
JP5271887B2 (ja) * | 2009-05-08 | 2013-08-21 | 国防科学研究所 | ライオセル系炭素繊維及び炭素織物の製造方法 |
CN101805943B (zh) * | 2010-04-21 | 2011-11-16 | 哈尔滨工业大学 | 一种中空碳纤维的制备方法 |
RU2520982C1 (ru) * | 2012-10-10 | 2014-06-27 | Открытое акционерное общество "Научно-исследовательский институт конструкционных материалов на основе графита "НИИграфит" | Способ карбонизации вискозных волокнистых материалов в процессе получения углеродных волокон |
FR2997097B1 (fr) * | 2012-10-22 | 2015-04-10 | Arkema France | Procede de fabrication d'une fibre de carbone, materiau precurseur utilise par le procede et fibre de carbone obtenue. |
FR3083547B1 (fr) | 2018-07-09 | 2021-07-30 | Inst De Rech Tech Jules Verne | Fibre de carbone et procede de fabrication d’une telle fibre de carbone a partir de cellulose |
FR3096691B1 (fr) | 2019-05-29 | 2021-06-25 | Inst De Rech Tech Jules Verne | Procédé de fabrication d’une fibre de carbone à partir d’une fibre de cellulose |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3174895A (en) * | 1960-09-07 | 1965-03-23 | Union Carbide Corp | Graphite cloth laminates |
US3628985A (en) * | 1965-10-23 | 1971-12-21 | Owens Illinois Inc | Organopolysiloxane impregnated fibrous sheet and method of producing same |
GB1130304A (en) * | 1966-01-12 | 1968-10-16 | V Nii Elektrotekhniki | Process for manufacture of flexible graphite material from rayon cord |
GB1222881A (en) * | 1967-01-06 | 1971-02-17 | Nippon Carbon Company Ltd | Process for the preparation of carbon fibers |
JPS4814821B1 (ru) * | 1970-03-30 | 1973-05-10 | ||
US3967029A (en) * | 1973-03-02 | 1976-06-29 | United Technologies Corporation | Boron-carbon alloy tape |
JPS5234025A (en) * | 1975-09-08 | 1977-03-15 | Japan Exlan Co Ltd | Process for producing carbon fibers having excellent performances |
FR2421982A1 (fr) * | 1978-04-03 | 1979-11-02 | Saint Gobain | Composition d'ensimage et fibres de verre traitees a l'aide de cette composition |
US4696827A (en) * | 1982-03-12 | 1987-09-29 | Sony Corporation | Silicon carbide-carbon composite molded product and process for manufacturing the same |
JPS5959976A (ja) * | 1982-09-22 | 1984-04-05 | 信越化学工業株式会社 | 炭化けい素被覆炭素繊維の製造方法 |
US5512359A (en) * | 1990-01-12 | 1996-04-30 | Alliedsignal Inc. | High flexural strength ceramic fiber reinforced silicon carboxide composite |
US5074912A (en) * | 1990-09-07 | 1991-12-24 | Dow Corning Corporation | Siloxane masonry water repellent emulsions |
FR2685694B1 (fr) * | 1991-12-30 | 1994-06-03 | Europ Propulsion | Procede pour la protection contre l'oxydation de produits en materiau composite contenant du carbone, et produits obtenus par le procede. |
RU2045472C1 (ru) * | 1992-09-04 | 1995-10-10 | Казаков Марк Евгеньевич | Способ получения углеродного волокнистого материала |
JPH11240779A (ja) * | 1998-02-27 | 1999-09-07 | Tokai Carbon Co Ltd | Si含有多孔質炭素材の製造方法 |
FR2801907B1 (fr) * | 1999-12-06 | 2002-03-01 | Snecma | Carbonisation de materiaux fibreux cellulosiques en presence d'un compose organosilicie |
-
1999
- 1999-12-06 FR FR9915327A patent/FR2801906B1/fr not_active Expired - Fee Related
-
2000
- 2000-05-12 UA UA2002064661A patent/UA72289C2/ru unknown
- 2000-12-05 MX MXPA02005625A patent/MXPA02005625A/es active IP Right Grant
- 2000-12-05 WO PCT/FR2000/003388 patent/WO2001042541A2/fr active Search and Examination
- 2000-12-05 JP JP2001544407A patent/JP4808351B2/ja not_active Expired - Lifetime
- 2000-12-05 AT AT00985406T patent/ATE265561T1/de active
- 2000-12-05 BR BRPI0016123-3A patent/BR0016123B1/pt not_active IP Right Cessation
- 2000-12-05 US US10/148,777 patent/US7175879B2/en not_active Expired - Lifetime
- 2000-12-05 DE DE60010347T patent/DE60010347T2/de not_active Expired - Lifetime
- 2000-12-05 EP EP00985406A patent/EP1268895B1/fr not_active Expired - Lifetime
- 2000-12-05 AU AU21833/01A patent/AU2183301A/en not_active Abandoned
- 2000-12-05 RU RU2002115275/04A patent/RU2258773C2/ru not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
EP1268895A2 (fr) | 2003-01-02 |
RU2258773C2 (ru) | 2005-08-20 |
BR0016123B1 (pt) | 2011-11-01 |
DE60010347D1 (de) | 2004-06-03 |
WO2001042541A2 (fr) | 2001-06-14 |
US20020182138A1 (en) | 2002-12-05 |
FR2801906B1 (fr) | 2002-03-01 |
UA72289C2 (ru) | 2005-02-15 |
MXPA02005625A (es) | 2004-09-10 |
ATE265561T1 (de) | 2004-05-15 |
WO2001042541A3 (fr) | 2002-01-17 |
US7175879B2 (en) | 2007-02-13 |
AU2183301A (en) | 2001-06-18 |
DE60010347T2 (de) | 2005-05-12 |
JP2003516476A (ja) | 2003-05-13 |
RU2002115275A (ru) | 2004-02-20 |
JP4808351B2 (ja) | 2011-11-02 |
BR0016123A (pt) | 2002-08-06 |
FR2801906A1 (fr) | 2001-06-08 |
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