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Publication numberUS3718493 A
Publication typeGrant
Publication dateFeb 27, 1973
Filing dateOct 28, 1970
Priority dateJun 4, 1968
Publication numberUS 3718493 A, US 3718493A, US-A-3718493, US3718493 A, US3718493A
InventorsJoo L, Mc Kee J, Shea F
Original AssigneeGreat Lakes Carbon Corp
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Process for the production of carbon filaments from coal tar pitch
US 3718493 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

United States Patent 3,718,493 PROCESS FOR THE PRODUCTION OF CARBON FILAMENTS FROM COAL TAR PITCH Louis A. Joo, Johnson City, John A. McKee, Elizabethton, and Frederick L. Shea, Johnson City, Tenn., assignors to Great Lakes Carbon Corporation, New York,

No Drawing. Original application June 4, 1968, Ser. No. 734,257, now Patent No. 3,595,946. Divided and this application Oct. 28, 1970, Ser. No. 34,896

Int. Cl. C08h 13/00; C0911 3/24 US. Cl. 106--273 R 1 Claim ABSTRACT OF THE DISCLOSURE CROSS-REFERENCES TO RELATE APPLICATIONS This application is a division of application S.N. 734,- 257, filed June 4, 1968, now US. Pat. No. 3,595,946.

Carbon fibers have been produced from organic polymer fibers such as rayon or polyacrylonitrile by subjecting the latter to a regulated carbonization, preceded, in the case of fusible polymers, by a controlled oxidation to an infusible state. A difiiculty with this type of approach has been the low yield of carbon available from synthetic polymers.

Satisfactory carbon fibers have also been made from molten decomposition products of synthetic polymeric materials such as polyvinylchloride, polyvinyl acetate, and from fusible carbon-yielding materials like blown asphalt and petroleum pitch. In this type of process, the fusible material is spun into fibers, oxidized and carbonized to yield carbon fibers possessing strengths of over 100,000 p.s.i. In some cases, it has been found necessary to condition the starting material by heat treatment to raise its molecular weight and render it more amenable to the further transformations just mentioned. In the case of coal tar pitch however, these measures have failed and the art does not provide any successful method for the satisfactory spinning of pitches of coal tar origin and for their subsequent conversion into useful carbon fibers having properties comparable to those possessed by carbon fibers from other raw materials.

It is an object of this invention to provide easily spinnable materials from coal tar pitches capable of being transformed into useful carbon fibers. It is a further object to provide a method by which said modified coal tar pitches can be oxidized and carbonized satisfactorily. Still another object is to provide from common industrial coal tar pitches carbon fibers with tensile strengths in the class of 100,000 p.s.i. and which also possess to a sufficient degree the other desirable properties generally associated with such refractory material.

SUMMARY OF THE PROCESS These and other objects which shall become evident from the detailed description of the invention, have been accomplished by removing from a coal tar pitch substantially all of the material therein which is insoluble and remains as a second phase at the spinning temperature. Before or after this operation, the pitch is heat treated and distilled in order to increase its average molecular weight by polymerization and by removal of low molecular weight components formed or already present in the pitch. Various oxidizing, dehydrogenating and polymerizing agents may be employed in a number of manners to expedite this process. The treated pitch is then melted and spun into air, the resulting filament being stretched and wound continuously in conventional textile manner. The pitch filament is oxidized in one or more stages in an oxidizing medium and then carbonized at a temperature in the vicinity of 1000 C. in an inert atmosphere. If desired, the resulting carbon filament may be graphitized by heating in an inert atmosphere at elevated temperatures.

DETAILED DESCRIPTION The raw materials from which the fibers of the invention are spun consist of commercially available high temperature coal tar pitches having a ring-and-ball softening point (A.S.T.M. method) within the range of to 250 C. Incidentally, all softening points in the text of this application are ring-and-ball softening points and all percentages are on a weight basis. Among the usable coal tar pitches, those preferred have a softening point within the range of to 200 C.

A critical operation in the transformation process of the invention is the removal of the quinoline insolubles from the coal tar pitch selected. Quinoline insolubles represent material which is not soluble in the pitch at spinning temperature or, in other words, Which forms an undesirable second phase. This removal is generally done before heat treating and distilling the pitch. This sequence of operations however is not binding, especially when a pitch of low quinoline insoluble content is employed. To accomplish the removal of the undesirable fraction, the pitch may be diluted in an appropriate solvent, filtered or centrifuged and recovered. The solvents usable for this purpose are generally speaking any aromatic liquid having a boiling point or range between about 200 and 400 C., provided that the major liquifiable portion of the coal tar pitch is soluble in it. Said liquid should also be removed from the filtered pitch solution at temperatures preferably not exceeding 300 C., either at atmospheric pressure or under reduced pressure. Examples of usable liquids which fit these specifications are light creosote oil, anthracene oil, phenanthrene, quinoline, highly aromatic petroleum fractions and the like.

The dilution of the pitch and the subsequent filtration can be carried out at any temperature Within a range g0- ing from the softening point of the pitch to about 300 C. Proportions of solvent to pitch vary with the viscosity of the substance at the temperatures selected. In general, a dilution of 1:1 at a temperature of about 200 C. has been found convenient. The diluted pitch is then filtered to remove the undissolved material. This may be accomplished in a number of manners with known equipment, provided of course that the foraminous member of this equipment can withstand the filtration conditions. Fritted glass and porous stainless steel septums having openings of about 10 microns in average diameter are satisfactory. The filtration process may be facilitated and improved in a conventional manner by additions of known filter aids to the pitch liquid. The number of actual filtrations and their timing may vary according to several factors such as viscosity of the pitch liquid, amount and nature of undissolved solids, temperature, pressure and the like. Sufiice it to say here that at least one filtration is required for the purpose of this invention and that it may be carried out on a liquid solvent diluted or undiluted pitch at any stage before the actual passage of the pitch through the filament-forming spinneret. After completion of the filtration, the solvent is removed by evaporation preferably under reduced pressure at about 150 C., in any event, at a temperature not exceeding 300 C. As mentioned previously, the separation of the undesirable second phase may be accomplished by centrifugation rather than filtration, although the latter technique is preferred in most instances.

The coal tar pitch to be used for spinning filaments is heat treated and distilled to improve its molecular weight range. Either or both of these treatments may be carried out, as indicated earlier, before, after or between filtrations. The pitch is distilled at a temperature within the range of about 280 to 305 C. to remove its lower molecular weight components. This may be accomplished by any conventional method including distillation under re duced pressure, steam distillation and so on, using any conventional equipment such as a molecular still and the like, provided the temperature limits are respected. The pitch is heat soaked at similar temperatures for a period of about 10 to 100 hours or more under pressures which may range from less than one atmosphere to more than one atmosphere. The actual length of this heat treatment depends of course on the nature of the pitch components as well as on other factors. Polymerization can also be favored by incorporating within the pitch various oxidizing, dehydrogenating and polymerizing agents which may shorten the heat treatment or lower the operating temperature. Among suitable materials which may accomplish these ends are included organic and inorganic peroxides and high boiling nitroaromatie compounds such as nitronaphthalene and 2,4-dinitrochlorobenzene, and the like. In any event, the heat treatment must be carried in such a manner and under such conditions, within the limits already described, that there is produced a spinnable pitch having a softening point or range within 230 and 320 C., and a quinoline insoluble content of less than 2%. Preferred pitches within these limits are those which soften between 240 and 260 C. and contain no second phase at spinning temperatures or below.

The heat treated coal tar pitch prepared in the manner described is then spun into a continuous filament through a nozzle or spinneret with an internal diameter appropriate for the thickness of filament required. For spinning, the pitch is melted at a temperature between its melting point and about 300 C. and the melt is extruded through the spinnerets orifice by sufiicient nitrogen pressure to achieve a satisfactory rate or by other conventional means such as a metering pump, a piston and the like. The actual pressure and temperature used depend on the properties of the heat treated pitch used as well as upon each other. In this respect, it has been found that a pitch of the type prescribed by this invention can be spun satisfactorily under a driving N pressure of about 80 p.s.i. through a perforated stainless steel septum with pores averaging 10 microns or less and a spinneret orifice of 1.5 mm. in length and 0.3 mm. in diameter. More than one orifice may of course be employed. The filament produced emerges in air and is stretched and taken up on a conventional textile winder at a fixed speed, e.g. at 250 to 300 meters per minute. Filaments with diameters ranging from about 5 microns and higher can thus be produced.

Extrusion of the filament at high temperature initiates an oxidation process which may be intensified by passing the filament through an oxidizing atmosphere for a length of time sufficient to create the infusibility required by the subsequent carbonization treatment. Suitable oxidizing media for this purpose include air; ozone in air; oxygen blended with air, flue gases or inert gases; vapors or mists of nitroaromatic compounds such as nitrobenzene, nitrophenol, alpha-nitronaphthalene, nitrotoluene, nitrochlorobenzene and the like; oxidizing gases such as sulfur dioxide, sulfur trioxide, nitric oxide and the like. Alternately, the filament may be cooled to a temperature below its fusing point and then passed through liquid oxi dizing baths of the above mentioned nitroaromatics or of other oxidizing liquids such as nitric acid, sulfuric acid, chromic acid, permanganate solutions and the like.

These various oxidizing treatments may be carried out in a continuous manner on the filament emerging from the spinning machine or they may be applied to batches of filament wound into packages. In such an eventuality, the support of the filament package must be of such nature and/or construction that it yields or collapses as the wound filament contracts during the oxidation process.

Papers cylinders have been found useful in this function.

The oxidation of filament Wound in packages must follow a fairly critical heating regime if the superimposed and adjacent loops of filament are not to fuse together. This regime will naturally vary with the pitch, its previous oxidation history and the type and quality of additive present, if any. The best heating rates and soaking temperatures for a given material are naturally difficult to determine since the fusion temperature of the pitch changes as the oxidation proceeds. Nevertheless, it has been established that a heat treated pitch of the type preferred, as described earlier, will yield filaments that are successfully oxidized by raising the temperature to C. in less than 15 minutes, a non-critical step; holding the filament at 100 for about 20 hours; raising the temperatures from 100 to 195 C. at a preferred rate of about 5 C./hour; holding the filament at the latter temperature for a period within the range of about 60 to about hours, the upper part of that range being preferred. It should be noted that with certain materials temperature increase rates of up to 10 C./hour may be tolerated. In any event, the temperature at any time during the oxidation treatment should preferably be not higher than 10 C. below the softening point of the pitch at the given time. This batch type oxidation is best carried out in a circulating oven through which passes a constant flow of air or oxygen containing gas, both fresh and recycled, pre-heated at the desired temperature.

The oxidized filament may then be cooled to room temperature or subjected immediately to carbonization. If cooling is elected, it should be gradual, the to 100 C. step being accomplished at about the same rate as the reverse step previously carried out, with the last 100 to room temperature adjustment taking about three hours.

The oxidized pitch filament is then converted to a carbon filament. This is accomplished in an oven or kiln provided with means for allowing sweeping of the reaction area with an inert gas, e.g. nitrogen scoured through hot coke. When Wound filament in packages is treated, the packages are placed in a sagger and, as the inert gas is allowed to sweep the package for example from bottom to top, the temperature of the kiln is raised according to the following typical cycle: from 30 to 100 C., when necessary, at the rate of 10/hour; from 100 to 500 C. at 5/hour and from 500 to 1100 C. at 10/hour. Cooling to room temperature also should be gradual, e.g. from 1100 to 30 C. in about 36 hours. As the 100 to 500 C. temperature range is the most critical in the carbonization process, special care need be exerted in controlling the heating rate through that range. As to the top carbonization temperature, it must be noted that useful carbon fibers may be produced from 700 C. for amorphous carbon filaments to as high as 2800+ C. if graphitic filaments are desired. Heating rates and holding times are no longer critical about 1100 C.

A graphite filament may be conveniently prepared by heating a carbon filament for about one hour in argon at above 1500 C.

Carbon filaments (1100 C.) of conventional textile lengths may be produced from coal tar pitch by the method just described, having a tensile strength of 80,000 to 130,000 p.s.i., a modulus of elasticity within the range of 4.5 to 5.2)(10 p.s.i., a volume resistivity in ohm-inch of 1200 to 1600 and an apparent density of about 1.65

g./cc. Such filaments, and their graphitic counterparts, are eminently suited as substrate in vapor phase depositions such as manufacture of boron filaments, heat resistant reinforcement in fiber-matrix composites, as well as in other similar applications where filamentary carbon is conventionally and advantageously employed.

A better understanding of the process of the invention may be obtained from the following example. This embodiment is provided for illustrative purposes only and must not be construed as limiting the invention beyond the scope of the claims that follow this specification.

EXAMPLE A coal tar pitch having a softening point of 187 C., Allied Chemicals Companys CP-275 grade 350, was dissolved at 180 C. in an equal weight of a light creosote oil fraction having a boiling range of 270 to 315 C. for 88% of its content. The solution was filtered with Dicalite Speedplus diatomaceous earth through a coarse 40 to 60p fritted glass plate, then through a 4.5 to 5.511. fritted glass plate. The filtrate was stripped to 130 C. under a pressure of 3 mm. 'Hg. The soluble pitch fraction was heat treated for hours at 280 to 305 C. pot temperature, under a 50 C. condenser in which about 17% of low melting solid fraction was collected at 2 mm. Hg. The heat treated soluble pitch remaining after this treatment had a softening point of approximately 256 C.

The modified coal tar pitch just described was spun through a spinneret having an orifice of 1.5 mm. in length and a diameter of 0.3 mm. The molten pitch at 287 C. was driven through the spinnert by a nitrogen pressure of 110 psi. The resulting pitch filament had a final diameter of about 30 microns, when stretched and taken up on a paper cylinder at the rate of 256 meters per minute.

The wound filament paper packages were then hung on graphite supports in an oven through which fresh and recycled air in a ratio of about 1:1 was constantly circulated while the temperature was raised and lowered in 100 to 40 C. 2.0

The total residence in the oxidizing oven was thus 178.25 hours.

The oxidized filament packages were then placed in a stainless steel sagger on the same type of graphite hangers as used in the oxidation step, and subjected to the following time-temperature regime while being constantly swept by nitrogen previously scoured through coke at process temperature:

Hours 40 to 100 C., 10/hour 6 100 to 500 C., 5/hour 80 500 to 1100 C., 10/hour 1l00 to ambient temperature 3 6 The resulting carbon monofilament was tested on an Instrom tester at a cro'sshead speed of 0.2 in./min., using 1" gauge lengths. It was found to possess a tensile strength of 127,400 p.s.i., an elongation at break of 2% and a modulus of elasticity of 5.1 X 10 p.s.i.-a1l these measurements being averages of at least 6 independent determinations.

The carbon monofilament had an average diameter of 25 microns and, as measured on 0.125 inch long samples, a volume resistivity of 1419 ,uohm-inch with a variation of 15.0%.

There was thus produced by the method of this invention a carbon filament from coal tar pitch, that has excellent mechanical and electrical properties as compared to what was heretofore taught by the art. It is evident that these properties may be maximized by the man skilled in the art while remaining within the scope of the invention as described in the foregoing specification and defined by the following claims.

We claim:

1. A preconditioned coal tar, fiber forming, spinnable pitch of softening point about 230 to 320 C. containing less than 2 percent by weight of insoluble material at spinning temperature and below.

References Cited UNITED STATES PATENTS 3,070,449 12/ 1962 Davies et a1 106-284 X 3,629,379 12/ 1971 Otani et a1. 26429 3,392,216 7/1968 Otani et a1. 26429 JOAN B. EVANS, Primary Examiner US. Cl. X.R.

Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3919376 *Dec 26, 1972Nov 11, 1975Union Carbide CorpProcess for producing high mesophase content pitch fibers
US3919387 *Dec 26, 1972Nov 11, 1975Union Carbide CorpProcess for producing high mesophase content pitch fibers
US3995014 *Oct 31, 1974Nov 30, 1976Union Carbide CorporationProcess for producing carbon fibers from mesophase pitch
US4026788 *Dec 11, 1973May 31, 1977Union Carbide CorporationProcess for producing mesophase pitch
US4032430 *Dec 11, 1973Jun 28, 1977Union Carbide CorporationProcess for producing carbon fibers from mesophase pitch
US4032607 *Sep 27, 1974Jun 28, 1977Union Carbide CorporationProcess for producing self-bonded webs of non-woven carbon fibers
US4066737 *Mar 2, 1973Jan 3, 1978Koppers Company, Inc.Method for making isotropic carbon fibers
US4225416 *Nov 20, 1978Sep 30, 1980Deutsche Gold- Und Silber-Scheideanstalt Vormals RoesslerProcess for the production of high quality carbon black forming material
US4243512 *Jun 19, 1979Jan 6, 1981Kureha Kagaku Kogyo Kabushiki KaishaProcess for preparation of pitch for producing carbon fiber
US4517072 *Nov 16, 1983May 14, 1985Domtar Inc.Process for modifying coal tar materials
US4604184 *Feb 4, 1985Aug 5, 1986Domtar Inc.Modified coal-tar pitch
US4986893 *Jan 4, 1990Jan 22, 1991Kureha Kagaku Kogyo Kabushiki KaishaProcess for producing pitch for carbon materials
US5238672 *Jun 20, 1989Aug 24, 1993Ashland Oil, Inc.Mesophase pitches, carbon fiber precursors, and carbonized fibers
US5501788 *Jun 27, 1994Mar 26, 1996Conoco Inc.Self-stabilizing pitch for carbon fiber manufacture
US5614164 *Sep 11, 1992Mar 25, 1997Ashland Inc.Production of mesophase pitches, carbon fiber precursors, and carbonized fibers
CN102732280A *Jul 9, 2012Oct 17, 2012遇秉武High-softening-point coal-tar pitch production method
CN102732280BJul 9, 2012Apr 16, 2014遇秉武High-softening-point coal-tar pitch production method
DE3703825A1 *Feb 7, 1987Aug 18, 1988Didier EngVerfahren und vorrichtung zum herstellen von kohlenstoff-fasern
EP0087749A1 *Feb 23, 1983Sep 7, 1983Mitsubishi Oil Company, LimitedPitch as a raw material for making carbon fibers and process for producing the same
EP0201213A2 *Apr 10, 1986Nov 12, 1986E.I. Du Pont De Nemours And CompanyStabilization of pitch fiber
Classifications
U.S. Classification106/273.1, 208/41, 264/165, 208/22, 106/284
International ClassificationD01F9/15, D01F9/145
Cooperative ClassificationD01F9/15
European ClassificationD01F9/15
Legal Events
DateCodeEventDescription
Apr 16, 1990ASAssignment
Owner name: AKZO N.V., ARNHEM, THE NETHERLANDS
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:GREAT LAKES CARBON CORPORATION;REEL/FRAME:005277/0858
Effective date: 19900103
Nov 20, 1989ASAssignment
Owner name: FORTAFIL FIBERS, INC., A DE CORP.
Free format text: RELEASED BY SECURED PARTY;ASSIGNOR:MANUFACTURERS HANOVER TRUST COMPANY;REEL/FRAME:005221/0871
Effective date: 19870724
Feb 8, 1989ASAssignment
Owner name: CHASE MANHATTAN BANK, N.A., THE, AS CO-AGENT
Free format text: SECURITY INTEREST;ASSIGNOR:GREAT LAKES CARBON CORPORATION;REEL/FRAME:005016/0550
Effective date: 19890112
Owner name: MANUFACTURERS HANOVER TRUST COMPANY, AS CO-AGENT
Mar 18, 1985ASAssignment
Owner name: MANUFACTURERS HANOVER TRUST COMPANY A NY CORP.
Free format text: SECURITY INTEREST;ASSIGNOR:GREAT LAKES CARBON CORPORATION, A DE CORP;REEL/FRAME:004376/0430
Effective date: 19850228