EP0099425B1 - Verfahren zur Herstellung einer von mesophasem Pech abstammenden Kohlenstoffgarns und -faser - Google Patents

Verfahren zur Herstellung einer von mesophasem Pech abstammenden Kohlenstoffgarns und -faser Download PDF

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Publication number
EP0099425B1
EP0099425B1 EP82200943A EP82200943A EP0099425B1 EP 0099425 B1 EP0099425 B1 EP 0099425B1 EP 82200943 A EP82200943 A EP 82200943A EP 82200943 A EP82200943 A EP 82200943A EP 0099425 B1 EP0099425 B1 EP 0099425B1
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EP
European Patent Office
Prior art keywords
yarn
thermoset
mesophase pitch
winding
bobbin
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Expired
Application number
EP82200943A
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English (en)
French (fr)
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EP0099425A1 (de
Inventor
David Arthur Schulz
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.)
BP Corp North America Inc
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BP Corp North America Inc
Union Carbide Corp
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Priority to DE8282200943T priority Critical patent/DE3273187D1/de
Priority to EP82200943A priority patent/EP0099425B1/de
Publication of EP0099425A1 publication Critical patent/EP0099425A1/de
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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
    • D01F9/145—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from pitch or distillation residues
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65H—HANDLING THIN OR FILAMENTARY MATERIAL, e.g. SHEETS, WEBS, CABLES
    • B65H2701/00—Handled material; Storage means
    • B65H2701/30—Handled filamentary material
    • B65H2701/31—Textiles threads or artificial strands of filaments
    • B65H2701/314—Carbon fibres

Definitions

  • the invention relates to a method for producing a mesophase pitch derived carbon yarn, wherein the term "mesophase pitch” means a pitch containing at least about 40% by weight mesophase as the minimum level for which the pitch is capable of forming a continuous anisotropic phase when dispersed by agitation or the like, comprising the steps of:
  • thermoset fibers took place by winding said fibers on a bobbin or roller, transporting the roller to a carbonizing furnace and then unwinding the fibers from the roller and move them through the carbonizing furnace along a linear path, at a substantially constant speed and under a certain tension. Carbonizing accordingly took place with the thermoset yarn extending linearly and subjected to tension.
  • the tension has been found in the prior art to be necessary to obtain good mechanical properties such as tensile strength and Young's modulus in the yarn and to avoid kinks and other surface defects of the fibers in the yarn.
  • thermoset mesophase pitch yarn reduces considerably during pyrolysis.
  • threadline breaking strength for a thermoset mesophase pitch yarn declines from its value at room temperature to about one-fourth of this value as the temperature of the yarn in an inert atmosphere is raised until a temperature of from about 700°C to about 800°C is reached. At higher temperatures, the breaking strength of the yarn increases.
  • Non-prepublished experiments were carried out in an endeavor to avoid the aforementioned problem of raduced thread-line breaking strength at the elevated temperatures by collecting the thermoset mesophase pitch yarn onto a bobbin and subsequently pyrolyzing and carbonizing the pitch yarn on the bobbin.
  • the carbon yarns obtained had broken fibers and surface defects and were not deemed satisfactory.
  • the bobbins used usually became damaged as a result of this heat treatment because of the force arising from the contraction of the thermoset yarn.
  • a bobbin made of fine grain graphite was used in order to have the bobbin compatible with the yarn at the elevated temperatures.
  • thermoset mesophase pitch yarn Even a coreless package of the thermoset mesophase pitch yarn was used in the experiments in order to attempt to avoid problems which arose because of the use of a bobbin. Nevertheless, the coreless package produced unsatisfactory carbon yarn having surface defects.
  • Purpose of the invention is to provide a method avoiding the above-mentioned drawbacks.
  • thermoset yarn takes place onto a bobbin which is thermally and mechanically stable at the temperatures used to pyrolize and carbonize said yarn and which is chemically compatible with said thermoset yarn at stages of transition of said thermoset yarn and subjecting said thermoset yarn, while remaining on said bobbin to the said predetermined heat treatment to pyrolize and carbonize.
  • the invention allows higher manufacturing rates than are possible according to prior art methods at lower costs and with fewer problems. Less effort by production workers is needed for the instant heat treatment and there is a more efficient use of energy for the invention as compared to the prior art methods.
  • the invention permits the production of exceptionally good carbon yarn as compared to the prior art methods, and the invention enables a good control on the mechanical properties of the carbon yarn.
  • the therm "pitch” is a carbonaceous residue consisting of a complex mixture of primarily aromatic organic compounds derived from the thermal treatment of organic materials. Pitch is solid at room temperature and exhibits a broad melting or softening temperature and exhibits a broad melting or softening temperature range. When cooled from the melt, pitch becomes solidified without crystallization.
  • the term "mesophase" is synonomous with liquid crystal; i.e. a state of matter which is intermediate between a crystal and an isotropic liquid. Ordinarily, material in this state exhibits both anisotropic and the liquid properties.
  • Pitches can contain varying amounts of mesophase.
  • the mesophase regions in the pitch are recognized by the optical anisotropy in the liquid state and the anisotropy is maintained in the solid state.
  • the invention is carried out using mesophase pitch having at least about 70% by weight mesophase.
  • the term "yarn" as used in the art describes a plurality of fibers. Generally, the number of fibers is at least about 1000 and usually about 2000. The number of fibers can be 5000 or more.
  • mesophase pitch yarn and "pitch yarn” are used herein to identify the plurality of mesophase pitch fibers or "as-spun" fibers which define a yarn.
  • thermosetting yarn is used herein to identify the pitch yarn which has been subjected to a thermosetting treatment.
  • thermoset yarn and “carbon yarn” are used herein respectively to identify the thermoset yarn which has been pyrolyzed and carbonized.
  • winding angle is used herein in connection with the operation of winding thermoset yarn onto a bobbin. In accordance with prior art usage this term refers to the angle defined by the portion of the yarn being wound onto the bobbin and a plane perpendicular to the axis of the bobbin.
  • the instant invention allows the production of mesophase pitch derived carbon yarn having an average Young's modulus of at least about 69x10 6 kPa for the individual carbon fibers in the carbon yarn.
  • the bobbin can take the form of a cylinder or a cylinder having end faces.
  • the bobbin comprises a body made of stainless steel, or a refractory alloy, or ceramic, or boron nitride, or preferably a graphite material.
  • the bobbin features a layer of compressible resilient carbon material such as carbon felt around the cylindrical portion in order to absorb stresses arising from the expansion of the bobbin during the heat treatment and the contraction of the thermoset yarn during the pyrolyzing and carbonizing treatment.
  • the cylindrical portion of the bobbin can have an inside diameter of about 7,6 cm and an outside diameter of 8,9 cm with a length of about 27,9 cm.
  • the carbon felt has a thickness of from about 6,4 mm to about 12,7 mm thick.
  • the instant invention is particularly significant in connection with commercial production of mesophase pitch derived carbon yarn having about 2000 fibers.
  • the handling of the yarn and the difficulties in maintaining acceptable qualities is demanding.
  • the tension on the thermoset yarn during the winding step is from about 7,35 Newtons to about 29,4 Newtons (75-300 g) and preferably from about 14,7 Newtons to about 19,6 Newtons (150-200 g).
  • thermoset yarn as it is wound on the bobbin The control over the amount of tension in the thermoset yarn as it is wound on the bobbin is not very important. If the tension is too low, the resulting loosely wound bobbin is difficult to handle in the manufacturing operations, and the fibers in the yarn do not develop the straightness required for good mechanical properties. If the tension is too high, the fibers near the core of the bobbin become distorted as well as other problems develop.
  • One of the embodiments of the invention teaches a heat treatment carried out by increasing the temperature by from about 50°C to about 100°C per hour until the temperature is about 1300°C for from about one to two hours.
  • a similar thread-line heat treatment is known.
  • This heat treatment will be referred to as in the art, as a "precarb” or “precarbonizing” although carbonizing actually takes place.
  • the carbon yarn obtained from this treatment possesses many characteristics which make it suitable for a range of commercial uses. If, however, improved mechanical properties such as tensile strength and Young's modulus are desired, then a thread- line treatment as used in the prior art is carried out by unwinding the yarn and sending it through the thread-line treatment at a temperature of about 2500°C. Surprisingly, this thread-line treatment can be carried out using relatively high tension with very few of the fibers breaking.
  • the precarbonizing treatment may be followed by a thread-line treatment using generally higher tensions than the tension used according to the prior art methods.
  • the use of higher tensions during the thread-line treatment generally results in carbon yarn having Young's modulus from 10% to 40% higher than the carbon yarn subjected to the same temperature treatment according to the prior art.
  • thermoset yarn goes through well known stages of transition as gasses are driven out of the fibers. These gasses can be corrosive and highly reactive so that the heating units must be designed to resist these gasses. To some extent, the tendency for the gasses to be reactive at 1300°C is less than typically higher pyrolyzing and carbonizing temperatures such as 2500°C.
  • the two step pyrolysis and carbonizing operation allows the second heating unit to be less resistant to attack so that the second heating unit can be a less expensive unit and the unit used generally has a longer useful operating life.
  • mesophase pitch yarn is thermoset by subjecting it to a temperature of from about 200°C to about 400°C in air or some other oxidizing atmosphere.
  • the winding of the thermoset yarn onto a bobbin can be carried out using a range of winding angles. It has been found that a relatively wide range of angles of from about 15° to about 30° can be used in connection with a bobbin having no end faces for the aforementioned precarb treatment which uses a maximum temperature of about 1300°C.
  • a zero degree or parallel winding should be used with a bobbin having end faces in order to avoid having the yarn fall off the bobbin at the ends.
  • the bobbin having parallel windings can be heat treated to about 3000°C to produce good quality yarn having a strength of more than about 2760x10 3 kPa and a Young's modulus of greater than about 690x10 6 kPa.
  • Fig. 1 shows the principal steps in the commercial production of carbon yarn from mesophase pitch.
  • Spinning apparatus 5 is used to spin 2000 mesophase pitch fibers with each fiber having a diameter of about 0,325 mm.
  • the mesophase pitch fibers form a mesophase pitch yarn 6 which enters thermosetting unit 7.
  • Thermoset yarn 8 is produced by the thermosetting unit 7 and is moved to pyrolyzing and carbonizing unit 9 for a heat treatment to produce carbon yarn 11 which is wound up on rolls in collection unit 12.
  • winding and unwinding operations onto and off of a cardboard bobbin are carried out for the thermoset yarn 8 between the units 7 and 9.
  • thermoset yarn 8 Attempts to move the thermoset yarn 8 through the unit 9 at relatively high rates have resulted in load fluctuations on the thermoset yarn 8 and this in turn has produced poor quality carbon yarn 11.
  • Fig. 2 shows a spinning apparatus 13 which produces 2000 mesophase pitch fibers to define a mesophase pitch yarn 14.
  • the mesophase pitch yarn 14 enters thermosetting unit 16 which produces thermoset yarn 17.
  • Collecting unit 18 collects the thermoset yarn 17 onto a bobbin.
  • Figs. 3A and 3B show two embodiments of bobbins suitable for carrying out the instant invention.
  • Bobbin 19 includes a body 21 and a carbon felt material 22 having a bias cut 23 wrapped around the body 21 and to provide a smooth and continuous joint.
  • the carbon felt material 22 can be attached to the body 21 with an adhesive or even "masking" tape 24.
  • the tape 24 at the high temperatures carbonizes and is only used to temporarily hold the carbon felt material 22 in place until the thermoset yarn is wrapped onto the bobbin 19.
  • the inside diameter of the body 21 is about 7,2 cm and the length of the body 21 is about 27,9 cm.
  • the carbon felt material 22 has a thickness of about 6,35 mm.
  • Fig. 3B shows a bobbin 25 which can also be used in connection with the instant invention.
  • Bobbin 25 differs from bobbin 19 in that it has end plates 26.
  • the bobbin 25 allows a zero angle or parallel winding of thermoset yarn without encountering the problem of the yarn falling off at the ends of the bobbin 24.
  • a bobbin containing thermoset yarn is subjected to a heat treatment in pyrolyzing and carbonizing unit 27.
  • a heat treatment for one embodiment of the invention no further heat treatment is carried out.
  • Another embodiment has pyrolyzed yarn 28 subjected to a thread-line treatment at about 2400°C in carbonizing unit 29. This produces carbon yarn 30 which is moved to collecting unit 31 which winds the carbon yarn 30 onto another bobbin for storage and handling.
  • the bobbins used were made from commercially available fine grain graphite.
  • a mesophase pitch yarn having 2000 pitch fibers each with a diameter of about 0,325 mm was produced and thermoset in accordance with conventional practices.
  • the thermoset yarn was collected onto a bobbin made from fine grain graphite and having an inside diameter of about 7,6 cm, a length of about 27,9 cm, and a carbon felt layer about 6,35 mm thick.
  • the bobbin had no end faces and the winding tension was about 14,7 Newtons (150 g).
  • a winding angle of about 20° was used.
  • the yarn collected was about 1828 cm in length and the pyrolyzing and carbonizing treatment was carried' out in a nitrogen atmosphere with the temperature being raised at the rate of about 50°C per hour until a temperature of 1300°C was reached and this temperature was held for about two hours.
  • the temperature was returned to room temperature and the pyrolyzed yarn was then moved through a threadline carbonizing unit which had an atmosphere of nitrogen and had a furnace temperature of about 2400°C in order to further carbonize the yarn.
  • the average line tension in the carbonizing unit was about 78,4 Newtons (800 g).
  • the examples 1 to 8 resulted in carbon yarns which exhibited excellent mechanical properties and were visibly well collimated and substantially free of frays.
  • a mesophase pitch yarn such as in Example 1 was made and wound onto a bobbin having end faces but otherwise similar to the bobbin used in Example 1. Parallel winding with a tension of about 19,6 Newtons (200 g) was used. The heat treatment rate was the same as in Example 1 except that the final temperature was about 3000°C. No thread-line treatment was used. The carbon yarn obtained had a tensile strength of about 2760x10 3 kPa and a Young's modulus of greater than 690X106 kPa.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Inorganic Fibers (AREA)

Claims (12)

1. Verfahren zur Herstellung eines von einem Mesophasen-Pech abgeleiteten Kohlenstoffgarns, wobei der Begriff "Mesophasen-Pech" ein Pech bezeichnet, das mindestens etwa 40 Gew.% Mesophase als Mindestgehalt enthält, bei dem das Pech in der Lage ist, eine kontinuierliche anisotrope Phase zu bilden, wenn es durch Rührung oder ähnliche Maßnahmen dispergiert wird,
das folgende Schritte umfasst:
Bildung einer Mehrzahl von Mesophasen-Pech-Fasern (6, 14) zur Definition eines Mesophasen-Pech-Garns, Wärmehärtung des Mesophasen-Pech-Garns zur Herstellung eines wärmegehärteten Garns (8, 17), Aufwickeln des wärmegehärteten Garns auf eine Spule (21, 25) und
Unterwerfen des wärmegehärteten Garns (8) unter eine vorbestimmte Wärmebehandlung in einer inerten Atmosphäre zur Pyrolyse und Carbonisierung des wärmegehärteten Garns,
dadurch gekennzeichnet, daß das Aufwickeln des wärmegehärteten Garns (8,17) auf eine Spule (19, 25) erfolgt, die thermisch und mechanisch stabil ist bei den zur Pyrolyse und Carbonisierung des Garns (8,17) verwendeten Temperaturen und die chemisch verträglich ist mit dem genannten wärmegehärteten Garn (8, 17) in Übergangsstufen des genannten wärmegehärteten Garns und dadurch, daß das genannte wärmegehärtete Garn (8, 17) während es auf der genannten Spule verbleibt (19, 25) der vorbestimmten Wärmebehandlung zur Pyrolyse und Carbonisierung unterworfen wird.
2. Verfahren nach Anspruch 1, bei dem die Spannung auf das genannte wärmegehärtete Garn (8, 17) während des Aufwickelns zwischen etwa 7,35 Newton und etwa 29,4 Newton (75 bis 300 g) beträgt.
3. Verfahren nach Anspruch 2, bei dem die Spannung auf das genannte wärmegehärtete Garn (8, 17) während des Aufwickelns zwischen etwa 14,7 und etwa 19,6 Newton (150 bis 200 g) beträgt.
4. Verfahren nach Anspruch 2, bei dem die Temperaturbehandlung das Anheben der Temperatur des genannten wärmegehärteten Garns (8, 17) auf etwa 1300°C umfasst.
5. Verfahren nach Anspruch 2, bei dem die Wärmbehandlung durch Anhebung der Temperatur um zwischen etwa 50°C und etwa 100°C pro Stunde durchgeführt wird, bis die Temperatur etwa 1300°C beträgt, und bei dem anschließend die Temperatur von etwa 1300°C für eine vorbestimmte Zeit aufrechterhalten wird.
6. Verfahren nach Anspruch 5, bei dem die Temperatur von etwa 1300°C für zwischen etwa 1 und etwa 2 Stunden aufrechterhalten wird.
7. Verfahren nach Anspruch 1, das außerdem das Abwickeln des pyrolysierten Garns (28) und das Unterwerfen des pyrolysierten Garns unter eine Fadenstrecken-Wärmebehandlung in einer inerten Atmosphäre umfasst.
8. Verfahren nach Anspruch 1, bei dem der Aufwickelschritt mit einem Wickwwinkel von zwischen etwa 15° und etwa 30° durchgeführt wird.
9. Verfahren nach Anspruch 1, bei dem der Aufwickelschritt mit annähernd parallelem Wickeln ausgeführt.
10. Verfahren nach Anspruch 1, bei dem das Mesophasen-Pech-Garn (6, 14) mindestens etwa 1000 Mesophasen-Pech-Fasern enthält.
11. Verfahren nach Anspruch 1, bei dem das Mesophasen-Pech-Garn (6, 14) mindestens etwa 2000 Mesophasen-Pech-Fasern enthält.
12. Verfahren nach Anspruch 1, bei dem das Mesophasen-Pech-Garn (6, 14) etwa 2000 Mesophasen-Pech-Fasern enthält, die Spannung auf das wärmegehärtete Garn während des Wickelns zwischen etwa 7,35 Newton und etwa 29,4 Newton (75 bis 300 g) beträgt, der WiεkeIschritt mit einem Wickelwinkel von zwischen etwa 15° und etwa 30° ausgeführt wird, und die Wärmebehandlung ausgeführt wird mit um etwa 50°C bis etwa 100°C pro Stunde bis auf etwa 1300°C ansteigender Temperatur, wobei anschließend die Temperatur von etwa 1300°C für etwa 1 bis 2 Stunden aufrechterhalten wird.
EP82200943A 1982-07-22 1982-07-22 Verfahren zur Herstellung einer von mesophasem Pech abstammenden Kohlenstoffgarns und -faser Expired EP0099425B1 (de)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DE8282200943T DE3273187D1 (en) 1982-07-22 1982-07-22 Method for producing a mesophase pitch derived carbon yarn and fiber
EP82200943A EP0099425B1 (de) 1982-07-22 1982-07-22 Verfahren zur Herstellung einer von mesophasem Pech abstammenden Kohlenstoffgarns und -faser

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Application Number Priority Date Filing Date Title
EP82200943A EP0099425B1 (de) 1982-07-22 1982-07-22 Verfahren zur Herstellung einer von mesophasem Pech abstammenden Kohlenstoffgarns und -faser

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EP0099425A1 EP0099425A1 (de) 1984-02-01
EP0099425B1 true EP0099425B1 (de) 1986-09-10

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EP82200943A Expired EP0099425B1 (de) 1982-07-22 1982-07-22 Verfahren zur Herstellung einer von mesophasem Pech abstammenden Kohlenstoffgarns und -faser

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0660451B2 (ja) * 1987-06-05 1994-08-10 株式会社ペトカ ピッチ系黒鉛繊維の製造方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4275051A (en) * 1979-01-29 1981-06-23 Union Carbide Corporation Spin size and thermosetting aid for pitch fibers
US4276278A (en) * 1979-01-29 1981-06-30 Union Carbide Corporation Spin size and thermosetting aid for pitch fibers

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3392216A (en) * 1963-11-01 1968-07-09 Kureha Chemical Ind Co Ltd Method for producing carbon structures from molten baked substances
US3919387A (en) * 1972-12-26 1975-11-11 Union Carbide Corp Process for producing high mesophase content pitch fibers
EP0014161B1 (de) * 1979-01-29 1983-03-30 Union Carbide Corporation Verfahren zur Behandlung eines Bündels von Multifilamentfasern aus Pech und eine Zusammensetzung zum Schmälzen dafür

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4275051A (en) * 1979-01-29 1981-06-23 Union Carbide Corporation Spin size and thermosetting aid for pitch fibers
US4276278A (en) * 1979-01-29 1981-06-30 Union Carbide Corporation Spin size and thermosetting aid for pitch fibers

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EP0099425A1 (de) 1984-02-01

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