THREE DIMENSIONAL WOVEN FABRIC OF PITCH-DERIVED CARBON FIBRES

Abstract: Three dimensional woven fabrics containing, at least as one component thereof, the carbon fibers obtained by thermosetting treatment and carbonization treatment carried out after melt-spinning of high softening point pitch and having a tensile strength of 15 - 250 Kgf/mm², elongation of 0.5 - 8.0% and modulus of elasticity of 400 - 40,000 Kgf/mm² and a capability of increasing both of their tensile strength and modulus of elasticity to 1.1 times or more of the values before additive heat-­ treatment by way of the additive heat-treatment carried out under a relaxed state of the said carbon fibers are provided, whereby carbon fibers having a tensile strength of 150 Kgf/mm² or more and a modulus of elasticity of 40,000 Kgf/mm² or more are attained. They are superior in abrasion-resist­ ing property, flexion-resisting property and scratch-­ resisting property and useful as one component of fiber composite materials in reinforcing plastics, metals, cements, ceramics, carbon materials, etc.

Description: This invention relates to three-dimensional woven fabrics of pitch-derived carbon fibers having superior qualities. More particularly, it relates to three-dimensional woven fabrics of pitch-derived carbon fibers which are incomplete in crystallization and orientation of graphite crystals and yet have capability of increasing their tensile strength and modulus of elasticity greatly by heat treatment carried out under relaxed state whereby growth of crystal and orientation structure proceed. This invention is directed to three dimensional woven fabrics which are difficult in weaving in case of high strength, high elasticity carbon fibers derived from pitch. This invention is directed to three-dimensional fabrics woven from components at least one of which is easy for working and is a pitch derived carbon fiber carbonized at lower temperature than generally used temperature. In case of lower carbonization fibers, three-dimensional weaving can be carried out which is difficult in case of higher carbonization fibers. In addition, since the lower carbonization fibers themselves are lower in cost, even when working loss is formed, proportion of influence given upon product cost is small. This is also an advantage of the lower carbonization fibers. The lower carbonization fibers of the present invention are stronger against bending of small radius of curvature compared with carbon fibers having higher grade of carbonization, and have superior characteristic properties because their bent portions receive stress relaxation by the carbonization treatment applied thereafter and show superior resistances to abrasion, flexion and scratching. Therefore, the three dimensional woven fabrics of the present invention show superior ability as reinforcement fabrics for various kinds of materials. This invention is directed to three-dimensional woven fabrics of pitch-derived carbon fibers having high modulus of elasticity, useful for fiber-reinforcement. Pitch-derived carbon fibers having high modulus of elasticity have been heretofore produced firstly by subjecting a pitch having a high softening point to melt-spinning, oxidizing the surfaces of resulting fibers to make them infusible, followed by carbonization carried out in an inert gas atmosphere. This method is disclosed in Japanese official gazette of examined application (Tokuko) 15728 of 1966. This is certainly a superior production method of pitch-derived fibers but according to the disclosed method, it is necessary to keep fibers in a stretched state at the time of carbonization to obtain fibers having high modulus of elasticity. Since thermoset pitch fibers are extremely brittle, it is difficult to hold them in a stretched state. It is considered actually to be impossible to obtain high elasticity fibers by this method. In order to work out a solution to this problem, a method in which optically anisotropic pitch is used, has been proposed as disclosed in Japanese official gazette of examined application (Tokuko) 8634 of 1974 and Japanese official gazette of unexamined application (Tokukai) 19127 of 1974. Optically anisotropic pitch is easily graphitizable material and shows superior properties as raw material for high strength, high elasticity carbon fibers. Particularly, there is no need of being kept in a stretched state at the time of carbonization, they are considered to be advantageous method in the point of cost and quality. Carbon fibers from optically anisotropic pitch can be easily made into a high strength, high elasticity state but on the other hand they have weak points, that they are liable to be flawed, e.g. liable to be broken at the time of working. Such weak points exist more or less in case of brittle fibers. Glass fibers, PAN-derived carbon fibers, etc. are coated by sizing agents to give lubricity and cohesiveness of bundles. In case of carbon fibers from optically anisotropic pitch, there is a tendency of repelling a sizing agent due to harmful effect of easily graphitizable property. Since uniform coating is difficult, shortages of lubricity and cohesiveness of bundles are also weak points. In order to solve these problems, Japanese unexamined patent application (Tokukai) 21911 of 1985 discloses a method in which light grade of carbonization is carried out at a temperature of 400 - 650°C after thermosetting. This method is effective to some-extent for keeping elasticity of carbon fibers small and for preventing them from being flawed but since carbonization degree is too light, there are problems in insufficiency of shape and dimensional stability and in sufficiency of strength for passing through a process such as weaving in which strong force is to be applied. Particularly in case of three-dimensional woven fabrics, since there is a stage in which bending is applied at a small radius of curvature at the time of weaving, there is a problem of difficulty of weaving for high strength, high elasticity carbon fibers which are highly carbonized or graphitized. In case of high elasticity fibers having an elongation less than 0.4% and a modulus of elasticity higher than 392 GPa (40,000 Kgf/mm²), simple fabrics such as plain woven fabrics can be woven but it has been found to be substantially impossible to weave three dimensional woven fabrics. The present invention relates to three-dimensional woven fabrics of carbon fibers having high elasticity, produced from an optically anisotropic pitch or a high softening point pitch having a carbonization characteristic property close to an optically anisotropic pitch. It has been difficult heretofore to produce such three dimensional woven fabrics because of brittleness of such high elasticity carbon fibers and shortage of lubricity and cohesiveness of bundles, etc. It is an object of the present invention to solve the above-mentioned points of problem. The present invention resides in three dimensional fabrics woven by using carbon fibers having good workability and low strength and low elasticity, obtained by mitigating the carbonization condition of pitch fibers. The carbonization of pitch fibers are generally carried out by heat-treatment under an inert gas atmosphere. It is usually carried out at a temperature 1200°C or higher till high strength can be obtained. In case where high modulus of elasticity is required, heat treatment is carried out at a temperature higher than 2000°C. It has been found, however, that workability of such high strength, high elasticity carbon fibers is not good and carbonization carried out at a lower temperature is preferable. This invention relates to woven fabrics containing, at least as one component thereof, the carbon fibers obtained by thermosetting treatment and carbonization treatment carried out after melt-spinning of an easily graphitizing pitch, such as an optically anisotropic pitch, capable of forming needle cokes upon dry distillation, which is characterized in that said woven fabrics are three-dimensional woven fabrics and that said carbon fibers have a tensile strength of from 147 to 2450 MPa (15 to 250 Kgf/mm²), an elongation of 0.5 to 8.0%, a modulus of elasticity of from 3.92 to 392 GPa (400 to 40,000 Kgf/mm²) and a capability of increasing both of their tensile strength and modulus of elasticity to 1.1 times or more of the above values by way of an additional heat-treatment carried out under a relaxed state of the said carbon fibers, whereby carbon fibers having a tensile strength of 1470 MPa (150 Kgf/mm²) or more and a modulus of elasticity of 392 GPa (40,000 Kgf/mm²) or more are attained. The pitch derived carbon fibers which constitute three-dimensional woven fabrics, as at least one component, are produced by thermosetting treatment and carbonization treatment carried out after melt-spinning of a high softening point pitch. A high softening point pitch, referred to in the present applicaton, is a pitch which is easily graphitizing such as optically anisotropic pitch. The easily graphitizing pitch forms needle cokes by dry distillation. Further, at the time of carbonization of pitch fibers, it produces high elasticity carbon fibers even at tensionless carbonization. The easily graphitizing pitch includes, besides optically anisotropic pitch, dormant mesophase pitch, and premesophase carbonaceous material which show similar graphitizing property. The carbon fibers used in the three-dimensional woven fabrics of the present invention have a tensile strength of 147 to 2450 MPa (15 - 250 Kgf/mm²), an elongation of 0.5 - 8.0% and a modulus of elasticity of 3.92 to 392 GPa (400-40,000 Kgf/mm²) and have a capability of increasing their tensile strength and modulus of elasticity to 1.1 times or more of the values before additive heat treatment, by the additive heat treatment carried out under a relaxed state whereby a tensile strength of 1470 MPa (150 Kgf/mm²) or more and a modulus of elasticity of 392 GPa (40,000 Kgf/mm²) or more are attained. Tensile strength smaller than this range is not preferable because fibers become liable to be flawed in working. Tensile strength greater than this range is not preferable because parts of the fibers in the fabrics forming loop such as selvedges of fabrics are liable to be fluffy and abrasion-resisting property is lowered. It is preferable that tensile strength is in the range of 196 - 1470 MPa (20 - 150 Kgf/mm²). Elongation lower than this range is not preferable because fibers becomes liable to be flawed in weaving. Elongation greater than this range is not preferable because shape and dimensional stability of woven fabrics become lower. It is preferable that elongation is in the range of 0.6 -5.0%. Increase of tensile strength and increase of modulus of elasticity are phenomena usually observed for easily graphitizable pitches but a tensile strength smaller than this range after increase of strength by additional heat-treatment under relaxed state are not preferable because fatigue-resisting property and oxidation-resisting property of fabrics are inferior. Fibers having a tensile strength smaller than this range after increase of strength, have less tendency of repelling sizing agent by the heat treatment and hence necessity of using the method of the present invention become less. It is preferable that tensile strength after additional heat-treatment is in the range of 1960 - 4410 MPa (200 - 450 Kgf/mm²). Fibers having an increase of modulus of elasticity smaller than this range are not preferable because fatique-resisting property and oxidation-resisting property are inferior and dimensional change at the time of weaving is large. It is preferable that the modulus of elasticity after heat-treatment is in the range of 392 GPa - 980 GPa (40,000 - 100,000 Kgf/mm²). The carbon fibers used in the three dimensional fabrics of the present invention have, preferably a specific gravity of 1.30 - 1.95, a specific electric resistance of 1 × 10⁻³ - 5×10⁸ Ω·cm, a stack height of graphite crystals Lc (002) of 0.8 - 3.2 nm (8 - 32 Å), an interlayer spacing distance d002 of graphite crystals of 0.34 - 0.35 nm (3.46 Å - 3.49 Å), and after strength and elasticity have been increased by heat treatment, a stack hight of graphite crystals Lc (002) of 3.6 nm (36 Å) or more, increase of stack height Lc (002) is 0.5 nm (5 Å) or more, interlayer spacing distance d002 of graphite crystals is 0.35 nm (3.46 Å) or less, and decrease of interlayer spacing distance d002 is 0.003 nm (0.03 Å) or more. Most preferably, specific gravity is 1.35 -1.80, specific electric resistance is 1 × 10⁻² - 5 × 10⁷ Ω·cm and after increase of strength and elasticity by heat treatment, stack height Lc (002) of graphite crystals is 7 - 24 nm (70 - 240 Å) and interlayer spacing distance d002 is 0.33 - 0.34 nm (3.36 - 3.44 Å). In the production of three dimensional woven fabrics of the present invention, preferably, after melt-spinning a high softening point pitch, resulting pitch fibers, wound up once on bobbins or the like or without winding, are placed on a transportation belt, and continuously introduced into an oxidative atmosphere at a temperature of 200 - 400°C to thermoset the said pitch fibers, and subsequently placed on a transportation belt and subjected to carbonization treatment in the atmosphere of an inert gas at a temperature of 400 - 2000°C until of the said pitch derived fibers reach 147 - 2,450 MPa (15 - 250 Kgf/mm²) in tensile strength, 0.5 - 8.0% in elongation, and 3.92 - 392 GPa (400 - 40,000 Kgf/mm²) in modulus of elasticity and if necessary, are wound up on bobbins or the like and transferred to a weaving process. An oiling agent and a sizing agent are provided after spinning and if necessary, further added after thermosetting or further after carbonization. The presence of these agents gives effectiveness of improving handling property at the time of winding up, weaving and various kinds of processing accompanying thereto even when these agents disappeared after carbonization. The pitch fibers placed on transportation belts are subjected to thermosetting preferably in the oxidative atmosphere by heating at 200 - 400°C. As for heating temperature, it is preferably to be at a lower temperature in the neighbourhood of an inlet, it is gradually increased and kept at a higher temperature at the neighbourhood of 400°C at an outlet rather than it is kept at a constant temperature. If an inlet temperature is too high, pitch reaches melting point and fibers melt. As oxidation velocity is greater in the neighbourhood of an inlet, temperature of pitch becomes higher than the atmosphere temperature by heat generation and pitch often causes adhesion. If necessary, a concentration of oxidative-gas in the neighbourhood of an inlet is lowered. Further, it is also possible to keep the concentration of oxidative gas higher in order to shorten thermosetting time. Thermosetting time varies according to difference of thickness of fibers. Since pitch derived fibers after completion of thermosetting are extremely weak, they cannot be subject to a treatment in which a force is applied to the fibers. Preferably, they are kept on a transportation belt and sent into a carbonization apparatus. During this time, it is possible to add an oiling agent and a sizing agent in the form of mist. Carbonization is carried out preferably at a temperature of 400 - 2000°C in an inert atmosphere until a tensile strength of pitch derived fibers reaches 147 - 2,450 MPa (15 - 250 Kgf/mm²), an elongation of 0.5 - 8.0% and a modulus of elasticity of 3.92 - 392 GPa (400 - 40,000 Kgf/mm²). In the beginning of carbonization treatment, it is preferable to start from the substitution of oxygenic atmosphere by an inert gas at a temperature in the neighbourhood of 400°C. If substitution by an inert gas is insufficient, such problems as leaning of fibers, insufficiency of increase of strength may occur. Treatment time varies according to the thickness of fibers but in the beginning, elevation of temperature is carried out slowly at a rate of 10 - 100°C/min. and at the same time, substitution by an inert gas is carried out sufficiently and in the end, it is preferable to keep a constant temperature for several seconds or several hundred seconds. Resulting fivers are wound up on bobbins or the like subsequently and transferred to weaving or a preparation stage thereof. In place of winding-up on bobbins or the like, it may also be received in cans or the like to transfer to the next stage. In case where resulting fibers are wound up on bobbins or the like or received in cans or the like from a transportation belt, it is necessary to pull out through rollers or the like. In this case, it is preferable to reverse the fiber layers on the transportation belt and then pull out and apply tension to correct the shape to straight line form. In order to reverse the fiber layers on a transportation belt in the direction of thickness, various kinds of processes may be considered, but it is most preferable to use a process in which a second belt is caused to contact the fiber layer, and after putting the fiber layer between both the belts, the top and the bottom are reversed, the fiber layers are placed on the second belt and resulting fibers are pulled out from the top thereof. When a tension is applied on the resulting fibers, since modulus of elasticity of carbon fibers is extremely large, it is difficult to make tension uniform with a usual tension applying apparatus. It is preferable to give resistance by the viscosity of fluid. It is particularly preferable to give resistance by passing through a liquid containing an oiling agent or a sizing agent. In this case, it is preferable to flow a liquid through a channel or a tube. The fibers thus obtained, differently from the fibers highly carbonized, have smaller modulus of elasticity, liable to be wetted with a liquid such as an oiling agent, a sizing agent or the like, and have superiority in cohesiveness of bundles, and superiority in workability to such works as those containing a step of bending at a small radius of curvature e.g. in weaving. Further since the fibers are of lower cost than fibers of advanced carbonization state, they are extremely advantageous in case of products which produce working loss. Since relaxation of strain occurs at the time of carbonization, the fibers of the present invention are superior in abrasion resisting property and fatique resisting peroperty of bent parts of small radius of curvature. Further they show difficulty in fluff forming by abrasion and superior in resistance to flexion and scratching. It is preferable that the carbon fibers of the present invention are subjected to carbonization treatment to turn to products after carrying out the above-mentioned working of weaving. It is also possible to carry out further graphitization treatment. In the weaving of the carbon fibers of the present invention, it is possible to do weaving with 100% carbon fibers of the present invention. It is also possible to do weaving by mixing with other carbon fibers or graphite fibers. As for other carbon fibers, pitchderived carbon fibers of advanced carbonization state, or PAN type carbon fibers may be used. As a way of mixing, it is preferable to use carbon fibers of advanced carbonization state to the parts where bending at small radius of curvature is not applied at the time of weaving. Example 1 A distillate fraction of residual oil of thermal catalytic cracking (FCC) having an initial fraction of 404°C and a final fraction of 560°C (converted to atmospheric pressure) is subjected to heat treatment at a temperature of 420°C for 2 hours while sending methane gas therein and further at a temperature of 320°C for 18 hours to grow mesophase and mesophase was separated by sedimentation taking advantage of difference of specific gravity. This pitch had an optically anisotropic portion of 96%, quinoline insoluble portion of 47% and toluene insoluble portion of 82%. This pitch was spun through a spinning hole having an enlarged part at an outlet. After an emulsion of an oiling agent is coated upon the spun fibers according to a common procedure, fibers are taken up at the rate of 270 m/min. and piled up on a transportation belt while giving waving motion so as to form spiral shape locus. Subsequently, resulting fibers are subjected to oxidation treatment in a furnace having a temperature of 200°C at an inlet and 370°C at an outlet to apply thermosetting. After providing an oiling agent in the shape of aerosol to the fibers which come out of a furnace and is kept on a transportation belt, the fibers were sent into a carbonization furnace. The temperature of the furnace inlet was 450°C and while elevating temperature at a rate of 5°C/min. till 600°C and 20°C/min. till 700°C, substitution of an atmosphere by an inert gas was carried out. After the treatment at 700°C for 45 seconds, the fibers were taken out from the furnace and by putting between the transportation belt and a second belt, the top and the bottom of the fibers were reversed and wound up on bobbins. Resulting fibers had a strength of 215.6 MPa (22 Kgf/mm²), an elongation of 2.8%, a modulus of elasticity of 7.7 GPa (785 Kgf/mm²), a specific gravity of 1.45 and a specific electric resistance of 2.3 × 10⁷ Ω·cm. Three dimensional woven fabrics were made by using yarns of 3000 filaments of the resulting fibers having a diameter of 10 µm, in 3 directions. Among the structures of x-component yarns (yarns to be used as weft) of 10 ends/25 mm × 11 layers, and y component yarns of 10 ends/25 mm × 10 layers and z component yarn of 10 ends/25 mm, the structure of x-component yarns and z-component yarns and the structure of y-component yarns and z-component yarns were made into 2 kinds of weaving, plain weaving and intertwined weaving. It was judged that working of weaving was smooth in every woven fabrics and weaving property was good. Comparative example 1 When the fibers of Example 1 were subjected to heat treatment at a temperature of 2000°C for 5 minutes under an argon atmosphere, the high strength, high elasticity fibers having a tensile strength of 2,107 MPa (215 Kgf/mm²), an elongation of 0.6% and a modulus of elasticity of 394 GPa (40,200 Kgf/mm²) were obtained. When the fibers of Example 1 were subjected to heat treatment at a temperature of 2800°C under an argon atmosphere for 2 minutes the high strength, high elasticity fibers having a tensile strength of 2,822 MPa (288 Kgf/mm²), an elongation of 0.4% and a modulus of elasticity of 705.6 GPa (72,000 Kgf/mm²) were obtained. These two kinds of high strength, high elasticity carbon fibers were processed as in Example 1 to obtain three-dimensional woven fabrics but weaving property was extremely bad. There were many breakage of yarns and the surfaces of the fabrics was fluffy and good woven fabrics could not be obtained. Example 2 Fibers were made by using the pitch same with that of Example 1 and at the same spinning condition with that of Example 1. The resulting fibers having been thermoset under the state piled up on a transportation belt, were subjected to carbonization treatment by changing the highest temperature of a carbonization furnace and then wound up on bobbins as in Example 1 and workability was evaluated by weaving. The result are shown in Table 1. Properties of fibers and weaving property of fibers processed by changing carbonization temperature Carbonization temperature (max) Tensile strength MPa (Kgf/mm²) Elongation % Modulus of elasticity GPa (Kgf/mm²) Weaving property plain weaving three-dimensional 600°C 88.2(9) 3.0 2.9 (300) × × 700°C 176.4(18) 3.6 4.9 (500) o o 800°C 705 (72) 1.2 58.8 (6,000) o o 1050°C 1441(147) 1.1 132.3 (13,500) o o 1400°C 1793(183) 0.8 222.5 (22,700) o o 1700°C 2009(205) 0.7 287.1 (29,300) o o 2200°C 2401(245) 0.5 478.2(48,800) o × 2700°C 2783(284) 0.4 695.8 (71,000) ▵ × The three dimensional woven fabrics of the pitch-derived carbon fibers of the present invention are materials which are difficult to be woven from pitch-derived carbon fibers having a high carbonization degree. Since the carbon fibers used in the three-dimensional woven fabrics of the present invention are resistant to a bending of small radius of curvature as compared with carbon fibers of higher carbonization degree, they have good weaving properties. Since the parts bent at the time of weaving show strain relaxation at the time of carbonization treatment carried out afterwards, they are superior in abrasion-resisting property, flexion resisting property and scratch resisting property. Moreover, they have an advantage of cheap cost. The three dimensional woven fabrics of pitch-derived carbon fibers of the present invention can be used, as one component of fiber-composite-material, in reinforcing plastics, metals, cements, ceramics, carbon materials or the like. It is preferable to subject woven fabrics to heat-treatment to increase their strength, elasticity or the like before turning into composite material in these cases. The three dimensional woven fabrics of the present invention can be turned to active-carbon by the heat-treatment in an oxidative atmosphere. The resulting three-dimensional active-carbon woven fabrics have good shape stability and can be used for removing various kinds of materials by adsorption. Further they can be used as carriers for catalyst.

Claims: Woven fabrics containing, at least as one component thereof, the carbon fibers obtained by thermosetting treatment and carbonization treatment carried out after melt-spinning of an easily graphitizing pitch, such as an optically anisotropic pitch, capable of forming needle cokes upon dry distillation, characterized in that said woven fabrics are three-dimensional woven fabrics and that said carbon fibers have a tensile strength of from 147 to 2450 MPa (15 to 250 Kgf/mm²), an elongation of 0.5 to 8.0%, a modulus of elasticity of from 3.92 to 392 GPa (400 to 40,000 Kgf/mm²) and a capability of increasing both of their tensile strength and modulus of elasticity to 1.1 times or more of the above values by way of an additional heat-treatment carried out under a relaxed state of the said carbon fibers, whereby carbon fibers having a tensile strength of 1470 MPa (150 Kgf/mm²) or more and a modulus of elasticity of 392 GPa (40,000 Kgf/mm²) or more are attained.

Inventors: ARISAWA, SANJI ARISAWA MFG. CO. LTD., ITO, TOSHIYUKI, NAKAJIMA, HIDEYUKI KASHIMA SEKIYU SHATAKU, 16-303, SUTO, YOSHINORI KASHIMA SEKIYU SHATAKU, 1-201
Applicants: PETOCA LTD.
Application year: 1987
Main classification: D01F9
IPC codes: D01F9, D03D15, D03D25