US3179605A - Manufacture of carbon cloth - Google Patents
Manufacture of carbon cloth Download PDFInfo
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- US3179605A US3179605A US230214A US23021462A US3179605A US 3179605 A US3179605 A US 3179605A US 230214 A US230214 A US 230214A US 23021462 A US23021462 A US 23021462A US 3179605 A US3179605 A US 3179605A
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- regenerated cellulose
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S264/00—Plastic and nonmetallic article shaping or treating: processes
- Y10S264/19—Inorganic fiber
Definitions
- Another object is to prepare carbon fibers from regenerated cellulose in the form of yarn and cloth having increased tensile strength.
- a further object is to device an improved procedure for forming carbon fibers from regenerated cellulose.
- Sodium generally in the form of salts, is introduced into the regenerated cellulose cloth or yarn during the processing and it has been found essential to limit the sodium content in the manner indicated. Certain special regenerated celluloses have a sodium content below 25 ppm. and it is not necessary to employ the instant washing procedure thereon.
- regenerated cellulose is intended to embrace fibers of viscose rayon, cuprammoniurn rayon and saponified cellulose ester rayon, e.g., saponified cellulose acetate rayon.
- regenerated cellulose preferably high tenacity rayons, in the form of cord, yarn, cloth or the like having a sodium content above 25 ppm. While the sodium content can be reduced to below 25 ppm. simply by copious washing with water, it has been found preferable to hasten the process utilizing the procedure in the flow sheet. Furthermore, while the most important factor is to reduce the sodium content below 25 ppm, most preferably below 10 ppm, it is also desirable to reduce the total ash below 200 ppm. and preferably below 50 ppm.
- the regenerated cellulose is first washed in water.
- the water most preferably contains a detergent.
- potassium and ammonium containing anion detergents can be used, e.g., potassium lauryl sulfate, potassium dodecyl benzene sulfonate, ammonium decyl benzene sulfonate, potassium sulfosuccinate, ammonium di (Z-ethylhexyl) sulfosuccinate, it is preferable to employ nonionic detergents such as Triton X-45, Triton X-ll4, Triton X-100, Triton X-102, Triton bl-101 and Triton N-l28.
- nonionic detergents such as Triton X-45, Triton X-ll4, Triton X-100, Triton X-102, Triton bl-101 and Triton N-l28.
- Tritons of the X series are the reaction products of t-octylphenol with ethylene oxide and the Tritons of the N series are reaction products of t-nonylphenol with ethylene oxide, i.e., the Tritons are alkylphenoxy polyalkoxyalkanols.
- Triton X-45 there are five ethylene oxide groups
- Triton X-114 there are 7 to 8 ethylene oxide groups
- Triton X-100 and Triton N-lOl there are 9 to 10 ethylene oxide groups
- Triton X-102 and Triton N-128 there are 12 to 13 ethylene oxide groups.
- ⁇ active agents where the ethylene oxide groups are replaced by propylene oxide groups, e.g., t-octylphenol oxypropylated with 10 propylene oxide groups.
- Other nonionic surface active agents include sorbitan sesquioleate, sorbitan-polyethylene oxide monolaurate, Ethofat 3 (the reaction product of ethylene oxide with a mixture of palmitic, st-earic, oleic and linoleic acid), Ethofat 15 (the reaction product of ethylene oxide with a mixture of caprylic acid, capric acid and lauric acid), Ethomid 8 (the reaction product of the amides of caproic, caprylic and capric acids with ethylene oxide), Ethomid 18 (the reaction product of the amides of palmitic, stearic and oleic acid with ethylene oxide), polyethylene glycol stearate (Myrj 45), tertiary dodecyl polyethylene glycol thi
- the detergent is used in an amount of 0.01 to 0.5% of the Wash water, usually 0.1%.
- the regenerated cellulose is preferably rinsed in water to remove the detergent.
- the acid wash contains a 1 to 10% solution of a water soluble organic or inorganic acid such as acetic acid, propionic acid, formic acid, oxalic acid, hydrochloric acid, phosphoric acid or sulfuric acid.
- a water soluble organic or inorganic acid such as acetic acid, propionic acid, formic acid, oxalic acid, hydrochloric acid, phosphoric acid or sulfuric acid.
- acetic acid or hydrochloric acid is employed.
- the regenerated cellulose is thoroughly washed with water.
- the acid is preferably neutralized first with ammonia prior to the water wash.
- the neutralization can be omitted but in such case considerably more Water is required in the Water Wash.
- the regenerated cellulose is then dried either at room temperature or more preferably in an oven at a temperature up to 212 F.
- the dried regenerated cellulose e.g., in the form of cloth or yarn, is then converted to carbonized fibers, e.g., as cloth or yarn, either in known manner such as shown in the Soltes Patent 3,011,981, December 5, 1961, or Abbott Patent 3,053,775, September 11, 1962, or by an improved prooedure as set forth below.
- the dried regenerated cellulose which has been purified by removal of the sodium compounds and other noncellulosic materials is heated in a nonoxidizing atmosphere in order to carbonize the fibers.
- a nonoxidizing atmosphere there can be used inert gases such as nitrogen, helium, argon or even a vacuum, e.g., 0.001 mm.
- reducing gases such as hydrogen.
- Such procedures are known in the art, such as Soltes and Abbott, for example.
- the use of ammonia as the gas is an improvement over the procedures which have been employed in the past.
- ammonia gas is preferably employed in the present process for forming carbon fibers in which regenerated cellulose having a sodium content above 25 ppm. is reduced to a sodium content below 25 p.p.m.
- ammonia gas it is also possible to use the ammonia gas to improve prior art processes such as those of Soltes or Abbott.
- the purified and dried regenerated cellulose in the nonoxodizing atmosphere is heated fairly rapidly, e.-g., in less than 2 minutes, to a temperature of 250 to 400 F., preferably between 300 and 400 F. It is then heated slowly at a temperature of 250 F. to 500 F., most preferably between 300 and 500 F. While the time can be as short as 2 hours, it is preferably at least 12 hours and can be as long as a week.
- the product is then gradually heated at a temperature of from 500 to 800 F. for 2 to 24 hours or longer, usually for 4 to 12 hours. Next, the temperature is raised from 800 to 1500 F. or above over a period of 2 to 1800 hours. At a top temperature of 1500 F.
- the product has 94% carbon, at a top temperature of 1800 -F. the product has 96.5 to 97.5% carbon, and at a top temperature of 2000" F. the product contains 98 to 99% carbon. If the final temperature is elevated to 3500 F. or above, e.g., 5000 F., the product is converted into graphite fibers or cloth.
- Example 1 Viscose rayon yarn having a sodium content of 100 ppm. was washed thoroughly with water until the sodium content was ppm. and the total ash content was below 50 p.p.m. The rayon was then dried at 212 F. The dry product was placed in an oven at 350 F. in a nitrogen atmosphere and heated at 350 to 500 F. for 24 hours. It was then heated in a nitrogen atmosphere at a temperature of 500 to 800 F. for 6 hours and finally heated in a nitrogen atmosphere at a temperature increasing from 800 to 1800 F. over a period of 4 hours to obtain a carbon fiber product having 96.5% carbon.
- Example 2 Wellington-Sears Fortisan-36 cloth, -i.e., instantaneously saponified cellulose acetate rayon (regenerated cellulose), having 3400 filaments in the yarn and having x 20 threads per square inch and having a sodium content above 50 p.p.rn. was washed with water containing 0.1% Triton X-l00, rinsed with water, washed with 2% aqueous acetic acid, neutralized with 6% aqueous ammonia and rinsed with water to give a cloth product having 22 ppm. of sodium. This product wasdried at 212 F. and then converted to carbonized cloth by heating in a nitrogen atmosphere in the manner indicated below.
- regenerated cellulose regenerated cellulose
- the dry purified saponified cellulose acetate rayon was placed in an oven at 400 F. and heated at 400 to 500 F. for 12 hours. It was then heated at a temperature of 500 to 800 F. for 6 hours and finally heated at a temperature increasing irom 800 to 1800 F. over 12 hours to obtain a strong carbon cloth having a carbon content of 97%, and a Mullen burst strength of 47 p.s.i.
- Example 3 phere to obtain a product which was even better than that of Example 2.
- Example 2 The process of Example 2 was repeated utilizing 2% hydrochloric acid in place of the 2% acetic acid with similar results.
- Example 5 The procedure of Example 2 was repeated but the re-' Example 6 The procedure of Example 2 was repeated but the acid was with a mixture of oxalic acid and acetic acid.
- the procedure of Example 2 was repeated but the acid was with a mixture of oxalic acid and acetic acid.
- Example 7 North American viscose rayon identified as Viscose CX658 was employed as the regenerated cellulose cloth. There were about 3400 filaments in the yarn and there were about 20 x 20 threads per square inch. The acid employed in the scouring was 5% acetic acid. The sodium content of the cloth after purification and prior to carbonization was 25 ppm. The final carbon cloth product had a Mullen burst strength of 15 psi.
- a process of preparing carbon fibers of increased strength comprising washing regenerated cellulose fibers selected from the group consisting of viscose rayon, cu-
- prammonium rayon and saponified cellulose acetate rayon having a sodium content above 25 ppm. with water until the sodium content is below 25 p.p.m., and then heating the regenerated cellulose in a nonoxidizing atmosphere, said heating being carried out at a temperature of 250 F. to 500 F. for from 2 hours to a week, and then at a temperature of 500 to 800 F. for 2 to 24 hours, and then at a temperature of 800 to 1500 F. for from 2 to 1800 hours to convert the fibers to carbon fibers.
- a process of preparing carbon fibers of increased strength comprising washing regenerated cellulose fibers selected from the group consisting of viscose rayon, cu-
- a nonoxidizing atmosphere selected from the group consisting of nitrogen, helium, argon, ammonia, and a vacuum
Description
April 20, 1965 E. o. OHSOL 3,179,605
MANUFACTURE OF CARBON CLOTH Filed Oct. 12, 1962 R EG ENE RATED CELLULOSE NON I I0 WASH ON RINSE IN WATER WASH WITH ORGANIC ACID NEL L A A E W'.I
AMMONIA WASH WITH WATER HEAT FAST TO 400 F.
HEAT SLOW 400E TO 500F.
HEAT GRADUALLY 500F. TO 800 F HEAT 800 F TO INVENTOR.
I500EOR ABOVE ERNEST O. OHSOL BY I? TIdEA/EVS United States Patent 3,179,605 MANUFATITURE 0F CARBUN CLOTH Ernest 0. Ohsol, Wihnington, Del., assignor to Haveg Industries, Inc, a wholly-owned subsidiary of Hercules Powder Company, New Castle, Del., a corporation of Delaware Filed Oct. 12, 1962, Ser. No. 230,214 12 Claims. (Cl. 252-502) This invention relates to the preparation of carbon fibers.
It has been proposed in the past to prepare carbon fibers from cellulosic materials, e.g., Edison Patent 470,- 925, or more especially from regenerated cellulose, e.g., Soltes Patent 3,011,981 and Abbott Patent 3,053,775. However, it has been found difficult to obtain reproducible, good quality, high strength carbon fibers, e.g., in the form of yarn or cloth, by present procedures. While good quality products are obtained in some runs, in other runs employing exactly the same conditions the quality is poor.
Accordingly, it is an object of the present invention to prepare good quality carbon fibers from regenerated cellulose, e.g., in the form of yarn, cloth and the like, with reproducible results.
Another object is to prepare carbon fibers from regenerated cellulose in the form of yarn and cloth having increased tensile strength.
A further object is to device an improved procedure for forming carbon fibers from regenerated cellulose.
Still further objects and the entire scope of applicability of the present invention will become apparent from the detailed description given hereinafter; it should be understood, however, that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.
It has now been found that these objects can be attained if regenerated cellulose fibers, preferably in the form of cloth, are washed to a sodium content below 25 parts per million (ppm) and preferably below ppm.
Sodium, generally in the form of salts, is introduced into the regenerated cellulose cloth or yarn during the processing and it has been found essential to limit the sodium content in the manner indicated. Certain special regenerated celluloses have a sodium content below 25 ppm. and it is not necessary to employ the instant washing procedure thereon.
As used in the present specification and claims the term regenerated cellulose is intended to embrace fibers of viscose rayon, cuprammoniurn rayon and saponified cellulose ester rayon, e.g., saponified cellulose acetate rayon.
The invention will be best understood with reference to the accompanying drawing which is a diagrammatic illustration of the invention.
There is provided regenerated cellulose, preferably high tenacity rayons, in the form of cord, yarn, cloth or the like having a sodium content above 25 ppm. While the sodium content can be reduced to below 25 ppm. simply by copious washing with water, it has been found preferable to hasten the process utilizing the procedure in the flow sheet. Furthermore, while the most important factor is to reduce the sodium content below 25 ppm, most preferably below 10 ppm, it is also desirable to reduce the total ash below 200 ppm. and preferably below 50 ppm.
The regenerated cellulose is first washed in water. The water most preferably contains a detergent. While potassium and ammonium containing anion detergents can be used, e.g., potassium lauryl sulfate, potassium dodecyl benzene sulfonate, ammonium decyl benzene sulfonate, potassium sulfosuccinate, ammonium di (Z-ethylhexyl) sulfosuccinate, it is preferable to employ nonionic detergents such as Triton X-45, Triton X-ll4, Triton X-100, Triton X-102, Triton bl-101 and Triton N-l28. The Tritons of the X series are the reaction products of t-octylphenol with ethylene oxide and the Tritons of the N series are reaction products of t-nonylphenol with ethylene oxide, i.e., the Tritons are alkylphenoxy polyalkoxyalkanols. In Triton X-45 there are five ethylene oxide groups, in Triton X-114 there are 7 to 8 ethylene oxide groups, in Triton X-100 and Triton N-lOl there are 9 to 10 ethylene oxide groups, and in Triton X-102 and Triton N-128 there are 12 to 13 ethylene oxide groups.
There can be used corresponding surface active agents where the ethylene oxide groups are replaced by propylene oxide groups, e.g., t-octylphenol oxypropylated with 10 propylene oxide groups. Other nonionic surface active agents include sorbitan sesquioleate, sorbitan-polyethylene oxide monolaurate, Ethofat 3 (the reaction product of ethylene oxide with a mixture of palmitic, st-earic, oleic and linoleic acid), Ethofat 15 (the reaction product of ethylene oxide with a mixture of caprylic acid, capric acid and lauric acid), Ethomid 8 (the reaction product of the amides of caproic, caprylic and capric acids with ethylene oxide), Ethomid 18 (the reaction product of the amides of palmitic, stearic and oleic acid with ethylene oxide), polyethylene glycol stearate (Myrj 45), tertiary dodecyl polyethylene glycol thioether (Nonionic 218), Pluronics (condensation products of ethylene oxide with polypropylene glycol), sorbitan monopalmitate, polyethylene glycol lauryl ether (Brij). The preferred nonionic detergents are the higher alkyl phenol-alkylene oxide addition products.
The detergent is used in an amount of 0.01 to 0.5% of the Wash water, usually 0.1%.
If a detergent is employed in the wash water, then the regenerated cellulose is preferably rinsed in water to remove the detergent.
This is followed by an acid wash, generally at a pH of between 1 and 5. The acid wash contains a 1 to 10% solution of a water soluble organic or inorganic acid such as acetic acid, propionic acid, formic acid, oxalic acid, hydrochloric acid, phosphoric acid or sulfuric acid. Prefferably acetic acid or hydrochloric acid is employed.
After the acid wash the regenerated cellulose is thoroughly washed with water. As indicated in the drawing, the acid is preferably neutralized first with ammonia prior to the water wash. The neutralization can be omitted but in such case considerably more Water is required in the Water Wash. The regenerated cellulose is then dried either at room temperature or more preferably in an oven at a temperature up to 212 F.
The dried regenerated cellulose, e.g., in the form of cloth or yarn, is then converted to carbonized fibers, e.g., as cloth or yarn, either in known manner such as shown in the Soltes Patent 3,011,981, December 5, 1961, or Abbott Patent 3,053,775, September 11, 1962, or by an improved prooedure as set forth below.
The dried regenerated cellulose which has been purified by removal of the sodium compounds and other noncellulosic materials is heated in a nonoxidizing atmosphere in order to carbonize the fibers. As the nonoxidizing atposphere there can be used inert gases such as nitrogen, helium, argon or even a vacuum, e.g., 0.001 mm. Also, there can be employed reducing gases such as hydrogen. Such procedures are known in the art, such as Soltes and Abbott, for example. Preferably, however, there is em- .ployed ammonia since superior results can be attained therewith. The use of ammonia as the gas is an improvement over the procedures which have been employed in the past.
'While ammonia gas is preferably employed in the present process for forming carbon fibers in which regenerated cellulose having a sodium content above 25 ppm. is reduced to a sodium content below 25 p.p.m., it is also possible to use the ammonia gas to improve prior art processes such as those of Soltes or Abbott.
The purified and dried regenerated cellulose in the nonoxodizing atmosphere is heated fairly rapidly, e.-g., in less than 2 minutes, to a temperature of 250 to 400 F., preferably between 300 and 400 F. It is then heated slowly at a temperature of 250 F. to 500 F., most preferably between 300 and 500 F. While the time can be as short as 2 hours, it is preferably at least 12 hours and can be as long as a week. The product is then gradually heated at a temperature of from 500 to 800 F. for 2 to 24 hours or longer, usually for 4 to 12 hours. Next, the temperature is raised from 800 to 1500 F. or above over a period of 2 to 1800 hours. At a top temperature of 1500 F. the product has 94% carbon, at a top temperature of 1800 -F. the product has 96.5 to 97.5% carbon, and at a top temperature of 2000" F. the product contains 98 to 99% carbon. If the final temperature is elevated to 3500 F. or above, e.g., 5000 F., the product is converted into graphite fibers or cloth.
It has been found desirable to use a final temperature of 1800 F. because the resulting fiber product, whether in the form of cord, yarn or cloth, is very strong and, in fact, has A the strength of the original regenerated cellulose prior to carbonization. Such carbonized products have a much higher strength than carbon fibers or cloths made (from rayons having higher sodium contents than 25 ppm.
Unless otherwise indicated, all parts and percentages are by weight.
Example 1 Viscose rayon yarn having a sodium content of 100 ppm. was washed thoroughly with water until the sodium content was ppm. and the total ash content was below 50 p.p.m. The rayon was then dried at 212 F. The dry product was placed in an oven at 350 F. in a nitrogen atmosphere and heated at 350 to 500 F. for 24 hours. It was then heated in a nitrogen atmosphere at a temperature of 500 to 800 F. for 6 hours and finally heated in a nitrogen atmosphere at a temperature increasing from 800 to 1800 F. over a period of 4 hours to obtain a carbon fiber product having 96.5% carbon.
Example 2 Wellington-Sears Fortisan-36 cloth, -i.e., instantaneously saponified cellulose acetate rayon (regenerated cellulose), having 3400 filaments in the yarn and having x 20 threads per square inch and having a sodium content above 50 p.p.rn. was washed with water containing 0.1% Triton X-l00, rinsed with water, washed with 2% aqueous acetic acid, neutralized with 6% aqueous ammonia and rinsed with water to give a cloth product having 22 ppm. of sodium. This product wasdried at 212 F. and then converted to carbonized cloth by heating in a nitrogen atmosphere in the manner indicated below. The dry purified saponified cellulose acetate rayon was placed in an oven at 400 F. and heated at 400 to 500 F. for 12 hours. It was then heated at a temperature of 500 to 800 F. for 6 hours and finally heated at a temperature increasing irom 800 to 1800 F. over 12 hours to obtain a strong carbon cloth having a carbon content of 97%, and a Mullen burst strength of 47 p.s.i.
Example 3 phere to obtain a product which was even better than that of Example 2.
The process of Example 2 was repeated utilizing 2% hydrochloric acid in place of the 2% acetic acid with similar results.
Example 5 The procedure of Example 2 was repeated but the re-' Example 6 The procedure of Example 2 was repeated but the acid was with a mixture of oxalic acid and acetic acid. The
sodium content was only reduced to 26.6 p.p.m. The Mullen burst strength of the carbonized cloth was less than 19.
In another l'lll'l wherein the sodium content was only reduced to 23.4 ppm. the Mullen burst strength was only 11.
Example 7 North American viscose rayon identified as Viscose CX658 was employed as the regenerated cellulose cloth. There were about 3400 filaments in the yarn and there were about 20 x 20 threads per square inch. The acid employed in the scouring was 5% acetic acid. The sodium content of the cloth after purification and prior to carbonization was 25 ppm. The final carbon cloth product had a Mullen burst strength of 15 psi.
In another experiment when washing was carried out to a sodium content of 6.4 ppm. and the viscose cloth carbonized, the Mullen burst strength of the carbonized cloth was 62 psi. This further illustrates the importance of sodium removal.
I claim:
1. A process of preparing carbon fibers of increased strength comprising washing regenerated cellulose fibers selected from the group consisting of viscose rayon, cu-
prammonium rayon and saponified cellulose acetate rayon having a sodium content above 25 ppm. with water until the sodium content is below 25 p.p.m., and then heating the regenerated cellulose in a nonoxidizing atmosphere, said heating being carried out at a temperature of 250 F. to 500 F. for from 2 hours to a week, and then at a temperature of 500 to 800 F. for 2 to 24 hours, and then at a temperature of 800 to 1500 F. for from 2 to 1800 hours to convert the fibers to carbon fibers.
2. A process according to claim 1 wherein the regenerated cellulose fibers are in the form of cloth. 0
3. A process according to claim 1 wherein at least a portion of the water wash is an aqueous acid wash.
4. A process according to claim 3 wherein at least a portion of the Water wash is with water containing a nonionic detergent.
5. A process according to claim 1 wherein the regenerated cellulose fibers are washed to a sodium content below 10 ppm.
6. A process according to claim 5 wherein the regenerated cellulose fibers are in the form of cloth.
7. A process according to claim 1 wherein the nonoxidizing atmosphere is an inert gas.
8. A process according to claim 1 wherein at least a portion of the water wash is with a member of the group consisting of acetic acid and hydrochloric acid.
9. A process according to claim 8 wherein after the acid wash the regenerated cellulose is washed with aqueous ammonia.
10. A process according to claim 1 wherein the heating at the temperature of 500 F. and above is carried out in an ammonia atmosphere.
11. A process of preparing carbon fibers of increased strength comprising washing regenerated cellulose fibers selected from the group consisting of viscose rayon, cu-
pramrnonium rayon and saponified cellulose acetate rayon having a sodium content above 25 ppm. with water until the sodium content is below 25 p.p.m., and then heating the regenerated cellulose in a nonoxidizing atmosphere selected from the group consisting of nitrogen, helium, argon, ammonia, and a vacuum, said heating being carried out at a temperature of 250 F. to 500 F. for from 2 hours to a Week, and then at a temperature of 500 to 800 F. for 2 to 24 hours, and then at a temperature of 800 to 1500 F. for from 2 to 1800 hours to convert the fibers to carbon fibers.
6 12. A process according to claim 11 wherein the n0noxidizing atmosphere is ammonia vapor.
References Cited by the Examiner UNITED STATES PATENTS 3,011,981 12/6 1 Soltes 252502 3,053,775 9/62 Abbott 252-421 3,116,975 l/64 Cross et al 252-502 JULIUS GREENWALD, Primary Examiner.
Claims (1)
1. A PROCESS OF PREPARING CARBON FIBERS OF INCREASED STRENGTH COMPRISING WASHING REGENERATED CELLULOSE FIBERS SELECTED FROM THE GROUP CONSISTING OF VISCOSE RAYON, CUPRAMMONIUM RAYOND AND SAPONIFIED CELLULOSE ACETATE RAYON HAVING A SODIUM CONTENT ABOVE 25 P.P.M. WITH WATER UNTIL THE SODIUM CONTENT IS BELOW 25 P.P.M., AND THEN HEATING THE REGENERATED CELLULOSE IN A NONOXIDIZING ATMOSPHERE, SAID HEATING BEING CARRIED OUT AT A TEMPERATURE OF 250*F. TO 500*F. FOR FROM 2 HOURS TO A WEEK, AND THEN AT A TEMPERATURE OF 500 TO 800*F. FOR 2 TO 24 HOURS, AND THEN AT A TEMPERATURE OF 800 TO 1500*F. FOR FROM 2 TO 1800 HOURS TO CONVERT THE FIBERS TO CARBON FIBERS.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US230214A US3179605A (en) | 1962-10-12 | 1962-10-12 | Manufacture of carbon cloth |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US230214A US3179605A (en) | 1962-10-12 | 1962-10-12 | Manufacture of carbon cloth |
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| US3179605A true US3179605A (en) | 1965-04-20 |
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Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3297405A (en) * | 1963-11-21 | 1967-01-10 | Siemens Planiawerke Ag | Method of carbonizing animal fiber materials |
| US3304148A (en) * | 1963-06-17 | 1967-02-14 | Haveg Industries Inc | Carbon cloth annealing process |
| US3322489A (en) * | 1964-07-28 | 1967-05-30 | Lorraine Carbone | Process of graphitizing "polynosic" regenerated cellulose fibrous textile and resulting fibrous graphite textile |
| US3333926A (en) * | 1963-10-30 | 1967-08-01 | Union Carbide Corp | Process for carbonizing cellulosic textile materials |
| US3337301A (en) * | 1964-01-17 | 1967-08-22 | Havey Ind Inc | Process for carbonizing fibrous cellulosic materials |
| US3395970A (en) * | 1963-10-30 | 1968-08-06 | Deering Milliken Res Corp | Method of carbonizing polyacrylonitrile impregnated cellulose, cyanoethylated cellulose and acrylonitrile graft copolymerized cellulose textiles |
| US3454362A (en) * | 1965-03-16 | 1969-07-08 | Union Carbide Corp | Process for producing fibrous graphite |
| US3479151A (en) * | 1966-01-03 | 1969-11-18 | Hitco | Method of carbonizing fibrous cellulosic materials |
| US3479150A (en) * | 1965-07-14 | 1969-11-18 | Hitco | Carbonization method for cellulosic fibers |
| US3508871A (en) * | 1963-05-29 | 1970-04-28 | Carborundum Co | Carbonizing fibrous materials |
| US3539296A (en) * | 1969-06-16 | 1970-11-10 | Kimberly Clark Co | Method of making carbonized cellulose fibers for incorporation in electrically conductive paper |
| US3607541A (en) * | 1967-02-23 | 1971-09-21 | Lorraine Carbone | Process for producing pyrolytic carbon impregnated thermal insulating carbonized felt |
| US3661503A (en) * | 1969-05-29 | 1972-05-09 | Union Carbide Corp | Process for dehydrating cellulosic textile material |
| US3716331A (en) * | 1970-04-10 | 1973-02-13 | Union Carbide Corp | Process for producing carbon fibers having a high young's modulus of elasticity |
| US4388289A (en) * | 1977-05-26 | 1983-06-14 | Hitco | Method of removing alkali and alkaline earth metal impurities from oxidized pan material |
| US4541973A (en) * | 1983-04-21 | 1985-09-17 | Celanese Corporation | Production of ferrimagnetic spinel fibers |
| US4780301A (en) * | 1985-10-09 | 1988-10-25 | Mitsubishi Rayon Co., Ltd. | Process for producing carbon fiber |
| US20020190409A1 (en) * | 2001-06-18 | 2002-12-19 | Burdsall Charles W. | Method for reinforcing ceramic composites and ceramic composites including an improved reinforcement system |
| US20040009116A1 (en) * | 2002-07-12 | 2004-01-15 | Jean-Etienne Loncle | Method and installation for heat treating carbon bodies containing sodium |
| US20090246511A1 (en) * | 2008-03-25 | 2009-10-01 | Korea Institute Of Energy Research | Cellulose carbide material having graphite nanolayer and synthesis method thereof |
| US20110083953A1 (en) * | 2009-10-14 | 2011-04-14 | Reklaim, Inc. | Pyrolysis process and products |
| WO2017137285A1 (en) * | 2016-02-11 | 2017-08-17 | Basf Se | Method for producing carbon fibres from cellulose fibres treated with sulphonic acid salts |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3011981A (en) * | 1958-04-21 | 1961-12-05 | Soltes William Timot | Electrically conducting fibrous carbon |
| US3053775A (en) * | 1959-11-12 | 1962-09-11 | Carbon Wool Corp | Method for carbonizing fibers |
| US3116975A (en) * | 1961-02-08 | 1964-01-07 | Union Carbide Corp | Artificial graphite process |
-
1962
- 1962-10-12 US US230214A patent/US3179605A/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3011981A (en) * | 1958-04-21 | 1961-12-05 | Soltes William Timot | Electrically conducting fibrous carbon |
| US3053775A (en) * | 1959-11-12 | 1962-09-11 | Carbon Wool Corp | Method for carbonizing fibers |
| US3116975A (en) * | 1961-02-08 | 1964-01-07 | Union Carbide Corp | Artificial graphite process |
Cited By (32)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3508871A (en) * | 1963-05-29 | 1970-04-28 | Carborundum Co | Carbonizing fibrous materials |
| US3304148A (en) * | 1963-06-17 | 1967-02-14 | Haveg Industries Inc | Carbon cloth annealing process |
| US3333926A (en) * | 1963-10-30 | 1967-08-01 | Union Carbide Corp | Process for carbonizing cellulosic textile materials |
| US3395970A (en) * | 1963-10-30 | 1968-08-06 | Deering Milliken Res Corp | Method of carbonizing polyacrylonitrile impregnated cellulose, cyanoethylated cellulose and acrylonitrile graft copolymerized cellulose textiles |
| US3297405A (en) * | 1963-11-21 | 1967-01-10 | Siemens Planiawerke Ag | Method of carbonizing animal fiber materials |
| US3337301A (en) * | 1964-01-17 | 1967-08-22 | Havey Ind Inc | Process for carbonizing fibrous cellulosic materials |
| US3322489A (en) * | 1964-07-28 | 1967-05-30 | Lorraine Carbone | Process of graphitizing "polynosic" regenerated cellulose fibrous textile and resulting fibrous graphite textile |
| US3503708A (en) * | 1965-03-16 | 1970-03-31 | Union Carbide Corp | Graphite yarn |
| US3454362A (en) * | 1965-03-16 | 1969-07-08 | Union Carbide Corp | Process for producing fibrous graphite |
| US3479150A (en) * | 1965-07-14 | 1969-11-18 | Hitco | Carbonization method for cellulosic fibers |
| US3479151A (en) * | 1966-01-03 | 1969-11-18 | Hitco | Method of carbonizing fibrous cellulosic materials |
| US3607541A (en) * | 1967-02-23 | 1971-09-21 | Lorraine Carbone | Process for producing pyrolytic carbon impregnated thermal insulating carbonized felt |
| US3661503A (en) * | 1969-05-29 | 1972-05-09 | Union Carbide Corp | Process for dehydrating cellulosic textile material |
| US3539296A (en) * | 1969-06-16 | 1970-11-10 | Kimberly Clark Co | Method of making carbonized cellulose fibers for incorporation in electrically conductive paper |
| US3716331A (en) * | 1970-04-10 | 1973-02-13 | Union Carbide Corp | Process for producing carbon fibers having a high young's modulus of elasticity |
| US4388289A (en) * | 1977-05-26 | 1983-06-14 | Hitco | Method of removing alkali and alkaline earth metal impurities from oxidized pan material |
| US4541973A (en) * | 1983-04-21 | 1985-09-17 | Celanese Corporation | Production of ferrimagnetic spinel fibers |
| US4780301A (en) * | 1985-10-09 | 1988-10-25 | Mitsubishi Rayon Co., Ltd. | Process for producing carbon fiber |
| US20020190409A1 (en) * | 2001-06-18 | 2002-12-19 | Burdsall Charles W. | Method for reinforcing ceramic composites and ceramic composites including an improved reinforcement system |
| CN1329566C (en) * | 2002-07-12 | 2007-08-01 | Snecma固体燃料推进器公司 | Method and installation for heat treating carbon bodies containing sodium |
| FR2842191A1 (en) * | 2002-07-12 | 2004-01-16 | Snecma Propulsion Solide | PROCESS AND PLANT FOR HEAT TREATMENT OF SODIUM-CONTAINING CARBON PRODUCTS |
| WO2004007819A2 (en) * | 2002-07-12 | 2004-01-22 | Snecma Propulsion Solide | Method and installation for heat treatment of carbon products containing sodium |
| WO2004007819A3 (en) * | 2002-07-12 | 2004-04-08 | Snecma Propulsion Solide | Method and installation for heat treatment of carbon products containing sodium |
| US20040009116A1 (en) * | 2002-07-12 | 2004-01-15 | Jean-Etienne Loncle | Method and installation for heat treating carbon bodies containing sodium |
| US7351390B2 (en) | 2002-07-12 | 2008-04-01 | Snecma Propulsion Solide | Method and installation for heat treating carbon bodies containing sodium |
| US20090246511A1 (en) * | 2008-03-25 | 2009-10-01 | Korea Institute Of Energy Research | Cellulose carbide material having graphite nanolayer and synthesis method thereof |
| US8414861B2 (en) * | 2008-03-25 | 2013-04-09 | Korea Institute Of Energy Research | Carbonized cellulose material having graphite nanolayer and synthesis method thereof |
| US20110083953A1 (en) * | 2009-10-14 | 2011-04-14 | Reklaim, Inc. | Pyrolysis process and products |
| US8888961B2 (en) | 2009-10-14 | 2014-11-18 | Reklaim, Inc. | Pyrolysis process and products |
| US9777159B2 (en) | 2009-10-14 | 2017-10-03 | Reklaim, Inc. | Pyrolysis process and products |
| WO2017137285A1 (en) * | 2016-02-11 | 2017-08-17 | Basf Se | Method for producing carbon fibres from cellulose fibres treated with sulphonic acid salts |
| US10995429B2 (en) | 2016-02-11 | 2021-05-04 | Deutsche Institute Furtextil-Und Faserforschung Denkendorf | Method for producing carbon fibers from cellulose fibers treated with sulfonic acid salts |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AS | Assignment |
Owner name: CHAMPLAIN CABLE CORPORATION Free format text: CHANGE OF NAME;ASSIGNOR:HAVEG INDUSTRIES, INC.;REEL/FRAME:003845/0075 Effective date: 19801215 Owner name: CHAMPLAIN CABLE CORPORATION, DELAWARE Free format text: CHANGE OF NAME;ASSIGNOR:HAVEG INDUSTRIES, INC.;REEL/FRAME:003845/0075 Effective date: 19801215 |