US3784679A - Process for producing carbon fibres - Google Patents

Process for producing carbon fibres Download PDF

Info

Publication number
US3784679A
US3784679A US00137976A US3784679DA US3784679A US 3784679 A US3784679 A US 3784679A US 00137976 A US00137976 A US 00137976A US 3784679D A US3784679D A US 3784679DA US 3784679 A US3784679 A US 3784679A
Authority
US
United States
Prior art keywords
heat treatment
carbon fibres
pitch
fibres
producing carbon
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
Application number
US00137976A
Inventor
P Chiche
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Charbonnages de France CDF
Original Assignee
Charbonnages de France CDF
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Charbonnages de France CDF filed Critical Charbonnages de France CDF
Application granted granted Critical
Publication of US3784679A publication Critical patent/US3784679A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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
    • 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
    • D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
    • D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • D01F9/145—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from pitch or distillation residues
    • D01F9/15—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from pitch or distillation residues from coal pitch
    • 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

  • the present invention concerns a process for producing carbon fibres from coal-tar pitch or from other strongly aromatic distillation residues.
  • Carbon fibres have already been obtained from coal-tar pitch by subjecting the said pitch to 'a heat treatment at a moderate temperature and possibly to other treatments or conditioning, and thereafter spinning the pitch so treated at a temperature of the order of 300 C.
  • the fibres so obtained were subjected to oxidation to render them infusible, and then carbonized in air.
  • these processes result in fibres of a much inferior quality, and mechanical properties to those produced from textile (e.g. rayon or poly-acrylonitrile) filaments but the latter are generally expensive to produce.
  • iAll object of the present invention is to provide a process which allows an improvement in the quality of the fibres obtained from coal-tar pitch or from another strongly aromatic substance like coal-tar pitch.
  • Another object of the present invention is to provide improved fibres obtained from this process.
  • a process for the production of carbon fibres from a strongly aromatic distillation residue comprising subjecting the said residue to a heat treatment at a moderate temperature, a hydrocarbon polymer being added to the said residue, before or during the heat treatment, the
  • polystyrene polystyrene
  • polybicyclo[2,2,1]-heptene-2 rubbers, etc.
  • the filtered strongly aromatic pitch is heated, before spinning under conditions of temperature, and for 'a length of time, as well as with agitation, such that the obtained material contains no or only a little anisotropic material; in other words, the heat treatment is stopped at the latest at the beginning of the onset of the anisotropic phase.
  • the presence of anisotripic material can easily be evidenced by examination with a polarized light optical microscope (M. Ihnatowicz, P. Chiche, J. Deduit; S. Pregermain and R. Tournant, Carbon, 4, 41 (1966)).
  • This heat treatment can be achieved in a reactor provided with an agitation or stirring system and means for scavenging gases.
  • the scope of this invention includes carbon fibres made by the process as set forth above.
  • This pitch was previously filtered 'at C. over a bronze filter with mean pore size of 2,1 in order to separate out the solid and pseudo-solid particles that the pitch contains naturally.
  • melt-index 4 high densiy polyethylene
  • the resulting product was spun at 204 C. at a drawing speed of 450 m./minnte.
  • the thus prepared carbon fibres were measured to have a mean breaking strength of 60 kg./mm. and a Youngs modulus of 4600 l g./mm. for a diameter of 30
  • the total yield of the operations as described in Example 1 was 64% EXAMPLE 4 (NOT ACCORDING TO THIS lNVENTION)
  • the operating conditions were identical with those in Example 1, but here the pitch did not receive any additive.
  • the carbon fibres prepared in this way were measured to have 'a mean breaking strength of 24 kg./mm. and a Youngs modulus of 3300 kg./mm. for a diameter of 30 1.
  • Example 1 The total yield of the operations as described in Example 1 was 61% The advantages of the invention are thus apparent by comparing these properties with those of the fibres according to the invention described in Examples 1 to 3.
  • a process for the production of carbon fibres from a strongly aromatic distillation residue pitch comprising subjecting said pitch to a heat treatment at a temperature on the order of about 420 C., the product of the heat treatment being thereafter spun into fibres which are then oxidized and carbonized, the improvement comprising adding a hydrocarbon polymer in an amount suflicient to improve the mechanical properties of the carbonized fibres to said pitch no later than during said heat treatment, said hydrocarbon polymer being selected from the group consisting of polyethylene, polypropylene, polystyrene, polybicycle[2,2,l]-heptene-2 and rubber.

Abstract

A PROCESS FOR THE PRODUCTION OF CARBON FIBRES FROM COAL TAR PITCH OR FROM OTHER STRONGLY AROMATIC DISTILLATION RESIDUES SUBJECTED TO HEAT TREATMENT AT A MODERATE TEMPERATURE WHEREIN A HYDROCARBON POLYMER IS ADDED TO THE STARTING MATERIAL BEFORE OR DURING SAID HEAT TREATMENT WHICH IS FOLLOWED BY SPINNING, OXIDIZING, AND CARBONIZING. POLYETHYLENE, POLYPROPYLENE, POLYSTYRENE, POLYBICYCLO (2,2,1)HEPTENE-2, AND RUBBER ARE PREFERRED POLYMERS.

Description

United States Patent 3,784,679 PROCESS FOR PRODUCING CARBON FIBRES Pierre Chiche, Verneuil-en-Halatte, France, assignors to Charbonnages de France, Paris, France No Drawing. Filed Apr. 27, 1971, Ser. No. 137,976 Claims priority, applic7altigri7ll rance, May 19, 1970,
Int. Cl. C01b 31/07 Us. or. 423-447 11 Claims ABSTRACT OF THE DISCLOSURE The present invention concerns a process for producing carbon fibres from coal-tar pitch or from other strongly aromatic distillation residues.
Carbon fibres have already been obtained from coal-tar pitch by subjecting the said pitch to 'a heat treatment at a moderate temperature and possibly to other treatments or conditioning, and thereafter spinning the pitch so treated at a temperature of the order of 300 C. The fibres so obtained were subjected to oxidation to render them infusible, and then carbonized in air. However, these processes result in fibres of a much inferior quality, and mechanical properties to those produced from textile (e.g. rayon or poly-acrylonitrile) filaments but the latter are generally expensive to produce.
iAll object of the present invention is to provide a process which allows an improvement in the quality of the fibres obtained from coal-tar pitch or from another strongly aromatic substance like coal-tar pitch.
Another object of the present invention is to provide improved fibres obtained from this process.
According to the process of this invention, there is provided a process for the production of carbon fibres from a strongly aromatic distillation residue comprising subjecting the said residue to a heat treatment at a moderate temperature, a hydrocarbon polymer being added to the said residue, before or during the heat treatment, the
product of the heat treatment being thereafter spun into fibres which are then oxidized and carbonized.
Among the preferred polymers embodied in this invention and giving good results, one can mention natural or synthetic polymers such as polyethylene, polypropylene, polystyrene, polybicyclo[2,2,1]-heptene-2, rubbers, etc.
According to a preferred embodiment, the filtered strongly aromatic pitch is heated, before spinning under conditions of temperature, and for 'a length of time, as well as with agitation, such that the obtained material contains no or only a little anisotropic material; in other words, the heat treatment is stopped at the latest at the beginning of the onset of the anisotropic phase. The presence of anisotripic material can easily be evidenced by examination with a polarized light optical microscope (M. Ihnatowicz, P. Chiche, J. Deduit; S. Pregermain and R. Tournant, Carbon, 4, 41 (1966)). This heat treatment can be achieved in a reactor provided with an agitation or stirring system and means for scavenging gases.
One may alternatively heat the mixture to a distinctly lower temperature but the reduced de-volatilization or the volatilizing-ofi' of the material so obtained renders the oxidation treatments, necessary for making the filaments infusible before carbonization, more difficult.
'ice
The scope of this invention includes carbon fibres made by the process as set forth above.
The following examples will serve better to throw into relief the advantages of this invention.
EXAMPLE 1 A high temperature coal-tar pitch with the following characteristics was utilized:
Kraemer-Sarnow point C Density g /cm. 1.32 Index of volatile materials (according to the standard ATIC-02-60) percent 64.3 Elemental analysis in percentage by weight:
Carbon 93.02 Hydrogen 4.45 Oxygen 1.5 Nitrogen 0.7 Sulphur 0.3
This pitch was previously filtered 'at C. over a bronze filter with mean pore size of 2,1 in order to separate out the solid and pseudo-solid particles that the pitch contains naturally.
After adding 10% by weight of melt-index 4, high densiy polyethylene, this mixture was heated to 420 C. under constant agitation at a heating rate of 3 C./minute; the generated volatile materials were entrained in a stream of nitrogen flowing at 3 l./min.
The resulting product was spun at 204 C. at a drawing speed of 450 m./minnte.
The whole of this was then placed in a furnace and subjected to the following operational conditions:
Hours From room temperature to 250 C. in the presence of air at a heating rate of 05 C./minute 7.5 From 250 C. to 700 C. in the presence of nitrogen and in the absence of oxygen, at a heating rate of 05 C./minute 15 From 700 C. to 1000 C., at a heating rate of 2 C./minute 2.5
Total 25 The furnace was then allowed to cool naturally. The mechanical properties of the resulting carbon fibres were measured with the aid of an Instron press, under the following conditions:
Length of test-tube mm 50 Pulling speed cm./minute 0.05
'In this way a mean breaking strength of 55 kg./mm. was measured as well as a mean Youngs modulus of 4200 kg./mm. and a mean diameter of 30,11.
These values represent the averages taken from 7 readings effected on different filaments. The total yield of the operations comprising the filtering, de-volatilization, spinning, oxidation and carbonization was 65%.
EXAMPLE 2 The total yield of the operations as described in Ex-,
ample 1 was 66%.
3 EXAMPLE 3 The operating conditions were identical with those in Example 1, except that the polyethylene was replaced by a polystyrene.
The thus prepared carbon fibres were measured to have a mean breaking strength of 60 kg./mm. and a Youngs modulus of 4600 l g./mm. for a diameter of 30 The total yield of the operations as described in Example 1 was 64% EXAMPLE 4 (NOT ACCORDING TO THIS lNVENTION) The operating conditions were identical with those in Example 1, but here the pitch did not receive any additive.
The carbon fibres prepared in this way were measured to have 'a mean breaking strength of 24 kg./mm. and a Youngs modulus of 3300 kg./mm. for a diameter of 30 1.
The total yield of the operations as described in Example 1 was 61% The advantages of the invention are thus apparent by comparing these properties with those of the fibres according to the invention described in Examples 1 to 3.
I claim:
1. In a process for the production of carbon fibres from a strongly aromatic distillation residue pitch comprising subjecting said pitch to a heat treatment at a temperature on the order of about 420 C., the product of the heat treatment being thereafter spun into fibres which are then oxidized and carbonized, the improvement comprising adding a hydrocarbon polymer in an amount suflicient to improve the mechanical properties of the carbonized fibres to said pitch no later than during said heat treatment, said hydrocarbon polymer being selected from the group consisting of polyethylene, polypropylene, polystyrene, polybicycle[2,2,l]-heptene-2 and rubber.
2. A process as claimed in claim 1 wherein the said polymer is added before the heat treatment.
. 3. A process as claimed in claim 1 wherein the said polymer is a polyethylene.
4. A process as claimed in claim 1 wherein the said polymer is a polypropylene.
5. A process as claimed in claim 1 wherein the said polymer is a polystyrene.
6. A process as claimed in claim 1 wherein the said polymer is a polybicyclo[2,2,1]-heptene-2.
7. A process as claimed in claim 1 wherein the said polymer is a natural or synthetic rubber.
8. A process as claimed in claim 1 wherein the heat treatment is stopped before the onset of the anisotropic phase in the pitch.
9. A process as claimed in claim 1 wherein the heat treatment is stopped at the beginning of the onset of the anisotropic phase in the pitch.
10. A process as claimed in claim 1 wherein the said pitch is coal-tar pitch.
11. A process in accordance with claim 1 wherein said hydrocarbon polymer is used in an amount on the order of about 10% by weight.
References Cited UNITED STATES PATENTS 3,629,379 12/1971 Otani 423447 X 3,639,953 2/1972 Kimura et a1. 423447 3,607,672 9/1971 Schmitd 423447 3,392,216 7/-l968 Otani 26429 3,595,946 7/1971 000 et al 26429 3,107,153 10/ 1963 Boquist 423448 OTHER REFERENCES MacKay et al.: Modern Plastics, vol. 45, No. 2, 1968, pp. 147-150.
EDWARD J. MEROS, Primary Examiner U.S. Cl. X.R. 26429
US00137976A 1970-05-19 1971-04-27 Process for producing carbon fibres Expired - Lifetime US3784679A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FR7018171A FR2087413A5 (en) 1970-05-19 1970-05-19

Publications (1)

Publication Number Publication Date
US3784679A true US3784679A (en) 1974-01-08

Family

ID=9055708

Family Applications (1)

Application Number Title Priority Date Filing Date
US00137976A Expired - Lifetime US3784679A (en) 1970-05-19 1971-04-27 Process for producing carbon fibres

Country Status (11)

Country Link
US (1) US3784679A (en)
JP (1) JPS5040170B1 (en)
BE (1) BE766992A (en)
CA (1) CA958176A (en)
CH (1) CH526467A (en)
DE (1) DE2124636C3 (en)
FR (1) FR2087413A5 (en)
GB (1) GB1340099A (en)
IT (1) IT939003B (en)
LU (1) LU63163A1 (en)
NL (1) NL7106217A (en)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3852428A (en) * 1970-09-08 1974-12-03 Coal Industry Patents Ltd Manufacture of carbon fibres
US3903220A (en) * 1972-12-04 1975-09-02 Carborundum Co Method for producing carbon fibers
US3966887A (en) * 1971-11-08 1976-06-29 Charbonnages De France Process for production of carbon fibers and the resultant fibers
US4020145A (en) * 1973-01-18 1977-04-26 Celanese Corporation Carbon fiber production
US4070446A (en) * 1973-02-01 1978-01-24 Sumitomo Chemical Company, Limited Process for production of carbon fiber
DE3238849A1 (en) * 1981-10-23 1983-05-05 Nippon Oil Co., Ltd., Tokyo INITIAL SPEECH FOR CARBON FIBERS
US4460454A (en) * 1981-07-10 1984-07-17 Mitsubishi Oil Co., Ltd. Process for producing pitch for using as raw material for carbon fibers
US4793912A (en) * 1986-06-02 1988-12-27 Mitsubishi Oil Co., Ltd. Process for producing a pitch having a low softening point
US4801372A (en) * 1985-10-02 1989-01-31 Mitsubishi Oil Co., Ltd. Optically anisotropic pitch
US4902492A (en) * 1987-10-28 1990-02-20 Rutgerswerke Ag Novel spinning method
US5308598A (en) * 1990-02-01 1994-05-03 E. I. Du Pont De Nemours And Company Plexifilamentary fibers from pitch

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3037829C2 (en) * 1980-10-07 1983-08-25 Rütgerswerke AG, 6000 Frankfurt Process for the production of modified pitches and low-boiling aromatics or olefins and the use of these pitches

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3852428A (en) * 1970-09-08 1974-12-03 Coal Industry Patents Ltd Manufacture of carbon fibres
US3966887A (en) * 1971-11-08 1976-06-29 Charbonnages De France Process for production of carbon fibers and the resultant fibers
US3903220A (en) * 1972-12-04 1975-09-02 Carborundum Co Method for producing carbon fibers
US4020145A (en) * 1973-01-18 1977-04-26 Celanese Corporation Carbon fiber production
US4070446A (en) * 1973-02-01 1978-01-24 Sumitomo Chemical Company, Limited Process for production of carbon fiber
US4460454A (en) * 1981-07-10 1984-07-17 Mitsubishi Oil Co., Ltd. Process for producing pitch for using as raw material for carbon fibers
DE3238849A1 (en) * 1981-10-23 1983-05-05 Nippon Oil Co., Ltd., Tokyo INITIAL SPEECH FOR CARBON FIBERS
US4440624A (en) * 1981-10-23 1984-04-03 Nippon Oil Co., Ltd. Starting pitches for carbon fibers
US4801372A (en) * 1985-10-02 1989-01-31 Mitsubishi Oil Co., Ltd. Optically anisotropic pitch
US4793912A (en) * 1986-06-02 1988-12-27 Mitsubishi Oil Co., Ltd. Process for producing a pitch having a low softening point
US4902492A (en) * 1987-10-28 1990-02-20 Rutgerswerke Ag Novel spinning method
US5308598A (en) * 1990-02-01 1994-05-03 E. I. Du Pont De Nemours And Company Plexifilamentary fibers from pitch

Also Published As

Publication number Publication date
LU63163A1 (en) 1972-07-26
JPS5040170B1 (en) 1975-12-22
CA958176A (en) 1974-11-26
DE2124636B2 (en) 1978-06-29
BE766992A (en) 1971-10-01
DE2124636A1 (en) 1972-11-02
DE2124636C3 (en) 1979-02-22
IT939003B (en) 1973-02-10
CH526467A (en) 1972-08-15
NL7106217A (en) 1971-11-23
GB1340099A (en) 1973-12-05
FR2087413A5 (en) 1971-12-31

Similar Documents

Publication Publication Date Title
US4014725A (en) Method of making carbon cloth from pitch based fiber
US3716607A (en) Heat treatment of molten carbonaceous material prior to its conversion to carbon fibers and other shapes
US4208267A (en) Forming optically anisotropic pitches
US3784679A (en) Process for producing carbon fibres
Ko The influence of pyrolysis on physical properties and microstructure of modified PAN fibers during carbonization
US3595946A (en) Process for the production of carbon filaments from coal tar pitch
US3919387A (en) Process for producing high mesophase content pitch fibers
US4138525A (en) Highly-handleable pitch-based fibers
US3552922A (en) Method for the manufacture of carbon fiber
US3852428A (en) Manufacture of carbon fibres
KR960007714B1 (en) Ultra-high modulus and high tensile strength carbon fibers and their production
US3556729A (en) Process for oxidizing and carbonizing acrylic fibers
Boucher et al. Preparation and structure of Saran-carbon fibres
US4892641A (en) Process for the production of mesophase pitch
US3811927A (en) Process for vapor deposition on glassy-carbon substrate
EP0124062B1 (en) A method for the preparation of pitches for spinning carbon fibers
US3966887A (en) Process for production of carbon fibers and the resultant fibers
JPH01138223A (en) Preparation of raw material pitch for carbon material
JPS61132629A (en) Production of nonwoven fabrics of pitch activated carbon fiber
CA1055664A (en) Rapid thermosetting of carbonaceous fibers produced from mesophase pitch
JPS602352B2 (en) Production method of Primesoface carbonaceous material
JPS6256198B2 (en)
JPH0314624A (en) Production of carbon yarn
US4990285A (en) Balanced ultra-high modulus and high tensile strength carbon fibers
US4759839A (en) Process for producing pitch useful as raw material for carbon fibers