EP0383339A2 - Procédé de filage de fibres de brai - Google Patents

Procédé de filage de fibres de brai Download PDF

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Publication number
EP0383339A2
EP0383339A2 EP90103030A EP90103030A EP0383339A2 EP 0383339 A2 EP0383339 A2 EP 0383339A2 EP 90103030 A EP90103030 A EP 90103030A EP 90103030 A EP90103030 A EP 90103030A EP 0383339 A2 EP0383339 A2 EP 0383339A2
Authority
EP
European Patent Office
Prior art keywords
opening
capillary
diameter
area
spinneret
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.)
Granted
Application number
EP90103030A
Other languages
German (de)
English (en)
Other versions
EP0383339A3 (fr
EP0383339B1 (fr
Inventor
Uel Duane Jennings
Roger Allen Ross
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.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
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 EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of EP0383339A2 publication Critical patent/EP0383339A2/fr
Publication of EP0383339A3 publication Critical patent/EP0383339A3/fr
Application granted granted Critical
Publication of EP0383339B1 publication Critical patent/EP0383339B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D4/00—Spinnerette packs; Cleaning thereof
    • D01D4/02—Spinnerettes
    • 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
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/253—Formation of filaments, threads, or the like with a non-circular cross section; Spinnerette packs therefor
    • 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

Definitions

  • This invention relates to a process for producing pitch carbon fibers which avoids formation of cracks which run in the axial direction of the fibers.
  • This invention is capable of producing generally round cross-section fibers with spinnerets which are relatively simple to manufacture and maintain.
  • the fibers have high strength due to random microstructure which prevents axial cracking. This is true, even for fibers of large diameters. Strong large diameter continuous carbon fibers have not been available heretofore due to the difficulties in producing such fibers. Accordingly, this invention includes both continuous fibers which are strong and large in diameter, and the process of fiber preparation, which is useful for fibers of both large and small diameters.
  • Axial cracking in substantially round carbon fibers can be avoided by use of the configuration of the conduit of this invention through which the pitch is spun.
  • the process of this invention involves spinning mesophase pitch through a spinneret having a round cross-section discharge capillary, but having at its inlet an opening which has a high aspect ratio.
  • the opening may be trapeziodal, elliptical, a parallelogram, or the like, provided it is long and narrow. Rectangular openings are preferred. Aspect ratios (length divided by width of the opening) of at least than 3:1 are preferred, with ratios of at least 5:1 being more preferred.
  • the opening must be larger than the cross-sectional area of the capillary.
  • Ratios of these areas of at least 2:1 are preferred, with ratios of at least 8:1 more preferred.
  • a preferred process will employ a spinneret with a counterbore upstream of and larger in diameter than the capillary at its outlet, and at its inlet the high aspect ratio opening having an area smaller than the cross-­sectional area of the counterbore.
  • the area of the opening is preferably from 10% to 70% of the area of the counterbore, and more preferably in the range of 25 to 45% of the area of the counterbore.
  • the length of the smaller side of the rectangle is approximately equal to the length of the diameter of the capillary of the spinneret.
  • the process of this invention is sufficiently effective in preventing the formation of axial cracks in fibers that it can be used to prepare strong, continuous, substantially round cross-section, large diameter carbon fibers.
  • These fibers have a diameter of from 30 to 100 micrometers and a strength after stabilization and carbonization of at least 375 Kpsi minus the diameter of the fiber in micrometers. Fibers having a diameter of 40 to 80 micrometers are preferred.
  • Such large diameter fibers are useful in the reinforcement of metal, ceramic or plastic matrices.
  • Figure 1 shows in schematic cross-section a spinning pack useful in the practice of this invention.
  • the pack consists of spinneret 10, shim 15, distribution plate 17 and screen pack 19 supporting filtration medium 20, which is described in U.S. 3,896,028 (Phillips).
  • the screen and filtration medium are optional elements.
  • Associated support, gasketing, heating and enclosing means are not shown in Figure 1.
  • Molten pitch supplied externally flows through the pack elements in the reverse order and is successively filtered through 20, is directed to one of a plurality of spinneret counterbores 24 via one of a plurality of coaxial holes 18 in distribution plate 17, passes through the opening 16 in shim 15 which forms the flow of pitch into a ribbon configuration.
  • the pitch is then extruded through the spinneret capillary 22.
  • Refinements in the spinneret 10 consist of wide entrance 26 which has tapering neck 28 leading to counterbore 24.
  • Counterbore 24 communicates with capillary 22 via entrance 30 with tapering neck 32.
  • Figure 3 of US 4,576,811 describes in detail the capillary entrance 30 and features within the tapering neck 32.
  • FIG. 2 further details the alignment of high aspect ratio opening 16 (which in this preferred embodiment is rectangular) of shim 15 to the axis of capillary 22 in the spinneret 10.
  • This arrangement is repeated for each of the many capillaries in the spinneret, and provides the beneficial formation of molten pitch flow into a ribbon configuration in its path from the distribution plate 17 to the spinneret 10.
  • the pitch flow stream generally remains within a plane that includes the axis of the spinneret capillary 22.
  • the drawings show a shim plate separate from the body of the spinneret used to provide the beneficial flow configuring opening. However other arrangements in which the high aspect ratio opening is incorporated in the spinneret body are within the scope of this invention.
  • the opening provide a reduction in cross-sectional area of pitch flow, as compared to the splnneret counterbore area, of about 10-70%, with from about 25 to 45% preferred. If the flow configuring opening is too wide (i.e., the shim opening has too low an aspect ratio) the benefits of the invention may not be obtained. If the flow restriction is too great (i.e., the shim opening is too narrow) process continuity may be impacted.
  • the aspect ratio may be 25:1 or more, provided the continuous flow of pitch through the opening is not impeded.
  • the rectangular geometry is the preferred flow configuration, but other configurations providing substantially ribbon-like flow may be used.
  • the long relaxation time of pitch probably also accounts for a slight variation from circular cross-­sections observed in fibers produced by the process of this invention. While the fibers are substantially round, the fibers, particularly the larger diameter fibers, spun through a rectangular opening upstream of the round spinneret exhibit a slight oval shape. They have an aspect ratio of 1.1 or less. That is, the longer dimension of the cross-section is 1.1 or less larger than the shorter dimension of the cross-section.
  • fiber stabilization, carbonization and optional graphitization is carried out conventionally.
  • a finish (either fugitive or durable) may be applied to ease handling and/or provide protection.
  • Stabilization in air is generally conducted between 250 and 380 °C. and on bobbins (see, e.g., US 4,527,754) preferably following the procedure disclosed in US 4,576,810. Larger diameter fibers will require longer stabilization times; a useful "rule of thumb” is that one hour of stabilization time is required for each micron of larger fiber diameter. Accordingly, a 30 micron fiber would be stabilized for ca.
  • the yarns or fibers can be devolatilized or "precarbonized" in an inert atmosphere at temperatures between 800 and 1000 °C. so that subsequent carbonization may proceed more smoothly and that formation of strength-limiting voids is reduced or eliminated entirely. Precarbonization is usually accomplished with 0.1 to 1 minute. Carbonization in inert atmosphere is carried out at 1000 to 2000°C. and preferably between 1500-1950 °C. for about 0.3 to 3 minutes. At this point a surface treatment and/or finish application may be beneficial to improve fiber performance, e.g., adhesion, in its eventual application, e.g., in a composite.
  • Graphitization if desired, is usually accomplished in an inert atmosphere by heating between 2400 and 3300 °C., preferably between 2600-­3000 °C. for at least about a minute. During any of the above-mentioned heating steps, longer times of treatment do not appear to be detrimental.
  • a plot of tensile strength versus diameter for carbon fibers of the prior art exhibits a curved line with high tensile strengths for small fibers, declining as fiber size is increased. For fiber diameters larger than 30 micrometers the curve flattens, but continues to trend downward as fiber diameter is increased.
  • Midcontinent refinery decant oil was topped to produce an 850°F plus residue.
  • the residue analyzed 91.8% carbon, 6.5% hydrogen, 35.1% Conradson carbon residue and 81.6% aromatic carbon by C13 NMR.
  • the decant oil residue was heat soaked 6.3 hours at 740°F, and then vacuum deoiled to produce a heat soaked pitch. This pitch tested 16.4% tetrahydrofuran insolubles (1 gram pitch in 20 ml THF at 75°F).
  • the pitch so obtained was pulverized, fluxed with toluene (1:1 weight ratio of solvent to pitch) by heating to the reflux temperature for about one hour.
  • the solution was passed through a 1 micron filter, and admixed with sufficient toluene/heptane (98:2) ("anti-solvent") to provide (a) an 99:1 by volume toluene/heptane mixture and (b) an 8:1 mixed solvent/­pitch ratio, by volume/weight.
  • the mixture was cooled to ambient temperature and the precipitated solids were isolated by centrifugation.
  • the cake was washed with additional anti-solvent and then dried in a rotary-vacuum oven.
  • Several such batches were blended, melted at about 400°C, passed through a 2 micron filter, and extruded into pellets.
  • the pitch pellets have a quinoline insolubles (ASTM 75°C) of less than 0.1% by weight and are 100% mesophase, as determined by the polarized light microscopy method.
  • the pellets were remelted when fed to a screw extruder with an exit temperature of 350°C, spun at about 360°C through a 4 inch diameter/480 hole spinneret.
  • the holes are round and arrayed in 5 concentric rings (96 holes per ring) located in the outer 1/2 inch of the spinneret face.
  • Each hole has a counterbore diameter of 0.055 inch, a capillary diameter of 200 microns, a capillary length of 800 microns (L/D equals 4), and an entrance angle of 80/60 degrees, as defined in Riggs et al. U.S. Patent 4,576,811 (See particularly, Example 2).
  • a 0.005 inch thick shim is interposed between the spinneret and the distribution plate a 0.005 inch thick shim is interposed.
  • the shim has a plurality of 0.008 x 0.10 inch slots that align with each spinneret hole as shown in figure 2. These slots form the pitch into a ribbon-shaped flow
  • the spinneret is externally heated to about 360°C, and the spinning cell comprises an outer quench tube about 6 inches in diameter, 5 feet long, with top 6 inches screened to permit entry of quench air at room temperature. Aspiration is provided by a tapered (3 to 2-1/2 inches) center column that is 4 inches long.
  • a silicone oil finish supplied by Takemoto Oil and Fat Co. is applied to the air-cooled as-spun filaments or green fibers, which are wound at 550 yards per minute onto a spool disclosed in U.S. Patent 4,527,754 (Flynn).
  • Carbonization was carried out by combining the yarn from 6 stabilized packages mounted in a creel to form a 2880 filament tow (nominally "3K") forwarded at 12 feet/minute under the tension of its own weight (about 150 grams) through a 3 foot long precarbonization oven at 600-800°C, then through a 19 foot long, carbon-resistance oven having a 1000° - 1200°C entrance zone, a 1950°C carbonization zone, and an exiting 1000° - 1200°C zone.
  • the fibers were at carbonization temperatures for about 1 minute.
  • the carbonized yarn was next passed through a 19 foot long chamber containing dried, room temperature air admixed with 0.098% (980 ppm) of ozone supplied at a rate of 1 cfm.
  • the yarns are overlayed with a 1% solution of epoxy resin (CMD-W55-5003, sold by the Celanese Corporation) in water, using the method and apparatus shown in U.S. Patent 4,624,102 (Bell, Jr.).
  • the thus treated yarns were cured at 350°C and then cleaned by passing the yarn through the guide described and illustrated in U.S. Patent 4,689,947 (Winckler).
  • Ten representative bobbins of the carbonized yarn so produced were selected and single fiber tensile properties were determined at 1" gauge length following ASTM 3379 on 10 samples from each bobbin (average diameter was 9.4 microns). The average resulting properties were 478 Kpsi strength, 52 Mpsi modulus and 0.9% elongation.
  • Less than 1% of the filaments observed in photomicrographic cross-­section of the yarn bundles showed signs of longitudinal cracking.
  • the microstructure of the individual filaments was in all cases random, an unusual level of microstruc­tural control and homogeneity.
  • the pitch had a "predicted spin temperature” of 355 °C. vs. 346 °C. for the pitch used in Example 1.
  • the "predicted spin temperature” is the temperature at which the pitch exhibits a melt viscosity of 630 poises, measured using an Instron capillary viscometer.
  • the spinneret had 500 holes (vs. 480); and the entrance angle was 135 degrees (vs. 80/60).
  • the fibers were carbonized as in Example 1 then graphitized using the same equipment run such that the residence time at the highest temperature (2550 °C.) was about 30 seconds. Resulting graphite fibers averaged (25 breaks/2 bobbins) 609 Kpsi strength, modulus 135 Mpsi and elongation was 0.55% No longitudinal cracking was observed; the microstructure was "random".
  • Example 1 can be repeated as follows: Pitch similar to that used in Example 1 is employed.
  • the spinneret bores have the same configuration as in example 1 but are twice as large (i.e., the capillary is 0.016 in. in diameter, etc.).
  • the shim opening is rectangular and 0.010 in. wide.
  • Fibers spun will have a diameter of 48 micrometers and a strength greater than 327 Kpsi. Microscopic examination of the cross-section of the fibers will reveal random microstructure, and the fibers will have little or no axial cracking.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Fibers (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
EP90103030A 1989-02-16 1990-02-16 Procédé de filage de fibres de brai Expired - Lifetime EP0383339B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US31151189A 1989-02-16 1989-02-16
US311511 1989-02-16

Publications (3)

Publication Number Publication Date
EP0383339A2 true EP0383339A2 (fr) 1990-08-22
EP0383339A3 EP0383339A3 (fr) 1991-08-28
EP0383339B1 EP0383339B1 (fr) 1995-05-10

Family

ID=23207232

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90103030A Expired - Lifetime EP0383339B1 (fr) 1989-02-16 1990-02-16 Procédé de filage de fibres de brai

Country Status (7)

Country Link
EP (1) EP0383339B1 (fr)
JP (1) JP2897137B2 (fr)
KR (1) KR0140867B1 (fr)
AU (1) AU626176B2 (fr)
CA (1) CA2009528C (fr)
DE (1) DE69019193T2 (fr)
ES (1) ES2072324T3 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104047066A (zh) * 2014-07-01 2014-09-17 陕西天策新材料科技有限公司 一种中间相沥青熔融纺丝方法
EP4045703A4 (fr) * 2019-10-17 2024-04-17 Tangold Inc. Fabrication de fibres de carbone à hautes propriétés mécaniques

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4601875B2 (ja) * 2001-08-02 2010-12-22 新日鉄マテリアルズ株式会社 炭素繊維の製造方法
JP5708896B1 (ja) * 2013-07-30 2015-04-30 東レ株式会社 炭素繊維束および耐炎化繊維束
CN111830982A (zh) * 2020-07-16 2020-10-27 陕西理工大学 一种移动机器人编队与避障控制方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4576811A (en) * 1983-11-03 1986-03-18 E. I. Du Pont De Nemours And Company Process for adjusting the fiber structure of mesophase pitch fibers
JPH0781211B2 (ja) * 1983-11-10 1995-08-30 株式会社ペトカ 炭素繊維の製造方法
US4628001A (en) * 1984-06-20 1986-12-09 Teijin Limited Pitch-based carbon or graphite fiber and process for preparation thereof
US4859381A (en) * 1986-01-22 1989-08-22 Osaka Gas Company Limited Process for preparing pitch-type carbon fibers
US4859382A (en) * 1986-01-22 1989-08-22 Osaka Gas Company Limited Process for preparing carbon fibers elliptical in section

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104047066A (zh) * 2014-07-01 2014-09-17 陕西天策新材料科技有限公司 一种中间相沥青熔融纺丝方法
EP4045703A4 (fr) * 2019-10-17 2024-04-17 Tangold Inc. Fabrication de fibres de carbone à hautes propriétés mécaniques
US12371821B2 (en) 2019-10-17 2025-07-29 Thread Innovations Inc. Fabrication of carbon fibers with high mechanical properties

Also Published As

Publication number Publication date
EP0383339A3 (fr) 1991-08-28
JPH02242918A (ja) 1990-09-27
ES2072324T3 (es) 1995-07-16
JP2897137B2 (ja) 1999-05-31
DE69019193D1 (de) 1995-06-14
CA2009528C (fr) 2001-01-09
KR0140867B1 (ko) 1998-07-01
DE69019193T2 (de) 1995-10-12
KR900013119A (ko) 1990-09-03
CA2009528A1 (fr) 1990-08-16
AU626176B2 (en) 1992-07-23
EP0383339B1 (fr) 1995-05-10
AU4984490A (en) 1990-08-23

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