CN102766990B - Preparation method of high heat conductivity carbon fiber - Google Patents
Preparation method of high heat conductivity carbon fiber Download PDFInfo
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- CN102766990B CN102766990B CN201210228727.6A CN201210228727A CN102766990B CN 102766990 B CN102766990 B CN 102766990B CN 201210228727 A CN201210228727 A CN 201210228727A CN 102766990 B CN102766990 B CN 102766990B
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Abstract
The invention relates to a preparation method of high heat conductivity carbon fiber, which belongs to the technical field of manufacturing carbon fiber. The preparation method comprises the following steps of: firstly, performing vapor or liquid phase stabilizing processing on polyimide fiber, so that crosslinking solidification is realized on a polyimide polymer chain of the polyimide fiber; then performing carbonization on the stabilized fiber in nitrogen in a low temperature constraint condition; and finally, performing high temperature graphitization processing. The polyimide fiber is a linear polymer material, wherein an imide group is shown in the specification and has a highly preferred orientation along the fiber axis of the polymer chain. High heat conductivity GF (Glass Fiber) with high crystallinity and orientation can be obtained by using the preparation method disclosed by the invention.
Description
Technical field
The present invention relates to a kind of preparation method of high heat-conductive carbon fiber, belong to the preparing technical field of charcoal fiber.
Background technology
Along with the raising of quality of the life, the requirement of the lightweight of people to portable high-end entertainment electronics appliances, miniaturization (thin) is more and more higher; Meanwhile, also require the performance of these electronic equipments more and more higher, function is more and more.The requirement of this two aspect impels the critical piece (as CPU etc.) of these electronic equipments integrated degree is more and more higher, speed is more and more faster and volume is more and more less, thereby in running, produce more heat, cause machine overheated, make user's experience of these equipment not good, frequent deadlock even damaged.For making each parts normal operation, efficient of these equipment, these heats directed derivation timely.
Novel hypersonic vehicle needs to stand low-density hot-fluid (1MW/m in long-time (more than 1000S) in process under arms
2magnitude) continuous heating, always add heat very high.Meanwhile, the profile of this aircraft complexity also causes many privileged sites to stand relatively strong heating, makes the temperature of its large area thermal protection system different parts in flight course extremely inhomogeneous.This has proposed severe challenge to traditional ablative-type protective coating and non-ablation heat insulation type thermal protection system, USAF Promoting Experiment chamber has proposed the concept of heat management for this reason, in order to the hot-fluid of Comprehensive Control different parts, make high-temperature region hot-fluid to low-temperature space transmission, thereby reduce the thermo-lag difficulty in high-temperature region.At present Heat Conduction Material used is difficult to reach instructions for use at aspects such as proportion, high temperature resistant, directional heat conductance, thermal coefficient of expansion and thermal shock resistances as Ni based high-temperature alloy, ceramic matric composite etc. simultaneously, and application is subject to certain limitation.Therefore in the urgent need to developing a kind of novel High directional thermal conductivity material to meet the flourish requirement of aerospace science and technology.
Graphite material not only has lower density (2.26g/cm
3left and right) and excellent mechanical behavior under high temperature, also there is excellent thermal shock resistance and high thermal conduction characteristic, be to meet the high heat conduction management material of one that above-mentioned field requires.The high thermal conduction characteristic of graphite material comes from the high thermal conductivity coefficient having along the graphite flake layer direction of carbon hexagonal network structure composition (can reach 2500Wm in theory
-1k
-1), and perpendicular to the only 6Wm of thermal conductivity of graphite flake layer direction
-1k
-1.Therefore in the preparation process of high-heat conductivity graphite material, should make graphite flake layer arrange in the same direction as far as possible, and in use maximize favourable factors and minimize unfavourable ones, by suitable design, heat be transmitted in the direction.Most graphite flake layers are along fiber axis to the high-performance continuous graphite fiber (GF) of preferentially arranging, at fiber axis to thering is higher thermal conductivity.Can arrange (or braiding) and be combined into needed High directional thermal conductivity based composite material of carbon through suitable design.
The high heat-conductive carbon Precursors of Fibers using is at present mainly Mesophase Pitch Fibers, but the intensity of this kind of fiber extremely low (only several MPa) is highly brittle, and causes its serialization production process very loaded down with trivial details, and cost is very high, and domestic still none unit can produce so far.Therefore finding one differs from former research and development route and prepares high heat conduction GF and have very important significance.
Researcher finds to have polyimides (PI) polymeric membrane of high-orientation in the process of the high oriented graphite of preparation, can make the graphite film of high crystalline and high-orientation in inert atmosphere through pressurization charing, graphitization.The height-oriented PI films of employings such as Japan scientist Murakami are raw material, through cutting, stacked, compacting, charing, graphitization made thermal conductivity up to 1800Wm
-1k
-1block materials.In these researchs, for suppressing the effusion of a large amount of carbon containing small-molecule substances that the fracture when the heat treatment of PI strand causes, reduce the defect in film, need to apply high pressure and heating rate very slowly, preparation condition harshness.The method is difficult to prepare bulk sample mass production, and its application has been subject to larger restriction.If polyimides is spun into fiber, then heat treatment of fiber is made to high heat conduction GF, by expanding greatly its range of application, will have broad application prospects.And PI fiber is as high polymer fibre, its extension at break is usually above 10%, and intensity is greater than 100MPa, very easily realizes the serialization of high heat-conductive carbon fiber and produces.
PI fiber is owing to being subject to compared with high draft in spinning moulding process in preparation process, and its macromolecular chain is mostly along fiber axis preferred orientation.Therefore, the orientation of PI strand in fiber is compared with film, higher to the degree of orientation along fiber axis, arranges more regular; Owing to containing more aromatic rings on main chain, PI macromolecular chain is similar to the long band of a rigidity simultaneously, and aromatic rings is distributed on long wide of being with mostly.The arrangement mode of this aromatic rings is very similar to Mesophase Pitch Fibers.And the molecular weight of PI is high far beyond mesophase pitch, its strand along fiber axial height preferred orientation is also longer than mesophase pitch.This molecular structure may generate that size is larger, defect graphite lattice still less.
Summary of the invention
Object of the present invention be just to provide a kind of novel be the preparation method of polyimide-based high heat-conductive carbon fiber, correlative study yet there are no in any open report.
The present invention is with reference to the preparation method of high-performance PAN based carbon fiber and high heat conduction MP base GF, by PI fiber is carried out to stabilisation, charing, graphitization processing, and in heat treatment process, apply the pressure in the high orientation of drawing-off (tension force) replacement PI film carbonization process, obtain the high heat conduction GF with high-crystallinity, high-orientation.
The present invention prepares the method for high heat conduction polyimides based carbon fiber, it is characterized in that, comprises the following steps: first polyimide fiber is carried out to gas phase or liquid stable processing, make its polyimides macromolecular chain crosslinking curing; Then stabilisation fiber is carried out in nitrogen atmosphere to the charing under low temperature constraints, finally carry out high temperature graphitization processing.
Polyimide fiber described above is linear polymeric material, and wherein imide group is structural formula 1, and these macromolecular chains are along fiber axis to having height preferred orientation.
Structural formula 1
The preferred extension at break of polyimide fiber described above is greater than 4%, intensity is greater than 100MPa, and the axial preferred orientation degree of its macromolecular chain is higher than 60% simultaneously.
Gas phase stabilisation condition described above: draw ratio is 0-15%, under air atmosphere or oxygen atmosphere, rises to 300-450 DEG C with the speed of 3-10 DEG C/min by room temperature, then rises to 450-550 DEG C with the heating rate of 0.5-2 DEG C/min again, stops 1-60min.(two sections of above-mentioned heat treatment processes are 450 DEG C when different)
Liquid stable condition described above: liquid phase oxidation medium is the red fuming nitric acid (RFNA) (mass concentration 68%) under boiling condition, and the processing time is that 5-40min(optimal time is 8-30min), polyimide fiber after treatment need be cleaned and be dried with distilled water.
Low-temperature carbonization condition described above: draw ratio is 0-6%, high pure nitrogen atmosphere, pressure 0.1-6MPa, rises to 500 DEG C with 5-20 DEG C/min, then rises to 800-1200 DEG C with the heating rate of 1-5 DEG C/min, and the time of staying is 1-60min.
High temperature graphitization condition described above: draw ratio is 0-4%, high-purity argon atmosphere, temperature is 2400-3200 DEG C, the time of staying is 1-60min.
Above-mentioned high pure nitrogen atmosphere is preferably not less than 99.9% nitrogen.
The polyimide fiber that the present invention is used, those skilled in the art, can prepare by the method for preparing fiber of routine.As adopt following methods.
One-step method spinning polyimide fiber: two kinds of monomers of dianhydride and diamines are heated to 150 DEG C ~ 250 DEG C and obtain polyimides in high boiling solvent (as phenols).Taking polyimide solution as spinning slurry, wet method or dry wet method spinning polyimide fiber, fiber, after preliminary stretching, is removed after solvent, carries out hot-stretch processing (300 DEG C ~ 500 DEG C), can obtain polyimide fiber.
Two step method spinning polyimide fiber: the first step is that dianhydride and diamines are carried out to solution (low temperature) polycondensation in aprotic polar solvent (as dimethyl formamide), obtain polyamic acid solution, through wet method or dry wet method spray silk, obtain polyamic acid fiber.Second step be by polyamic acid fiber through chemical imidization or thermal cyclization, obtain polyimide fiber.The stretching process of fiber can carry out in the first step, also can in the process of second step imidizate, carry out, or each step is all carried out certain stretching.
Above-mentioned dianhydride used and diamines, be dianhydride and the diamines of the imide group that can obtain structural formula 1.
In the present invention, the main purpose of polyimides stabilisation is that to make the linear polymeric crosslinking curing of polyimides be three-dimensional polymeric molecule, makes it melting doubling phenomena can not occur in follow-up heat treatment process, has a strong impact on the performance of polyimides based carbon fiber.The mode of stabilisation comprises two kinds of gaseous oxidation and liquid phase oxidations: so-called gaseous oxidation is carried out oxidation cross-linked reaction to fiber exactly under oxidizing atmosphere (such as air, oxygen etc.); Liquid phase oxidation is carried out cross-linking and curing reaction exactly under strong oxidizer (red fuming nitric acid (RFNA) etc.) condition.
In the present invention, the low-temperature carbonization of polyimide fiber refers under inert atmosphere its stabilisation fiber is carried out to the heat treatment at 1000 DEG C, at this heat treatment stages, violent chemical reaction has occurred, and discharges a large amount of carbon containings, nitrogenous micromolecular material.If the small-molecule substance of these releases is overflowing too much of carbon containing class especially, the defect that makes fiber is increased, charcoal yield reduces, thereby greatly reduces the performance of polyimides based carbon fiber.Therefore necessary meticulous control technique, especially, for suppressing the excessive volatilization of little point of subclass material, need to apply certain tension force (or drawing-off) to stabilisation fiber, and carry out low-temperature carbonization under certain hyperbaric environment.
Graphitization in the present invention is in inert atmosphere, above-mentioned charing polyimide fiber to be heat-treated at 2400-3200 DEG C.Even higher for making in polyimides based carbon fiber graphite microcrystal remain unchanged along fiber axis to the degree of orientation, in graphitizing process, fiber is applied to certain tension force (drawing-off).
The present invention compared with prior art has following advantages:
With other Carbon fiber precursor as compared with polyacrylonitrile fibre or viscose, aromatic rings on the macromolecular chain of polyimide fiber substantially in same plane, therefore more easily develops into that graphite microcrystal is larger, fiber axis is to the higher high heat-conductive carbon fiber of the degree of orientation;
2. more easily realize industrial continuous production.The high heat-conductive carbon Precursors of Fibers using is at present mainly Mesophase Pitch Fibers, but its intensity extremely low (only several MPa) is highly brittle, and causes its serialization production process very loaded down with trivial details, and cost is very high, and domestic still none unit can produce so far.And the extension at break of polyimide fiber is usually above 4%, intensity is greater than 100MPa especially, therefore with reference to the syntheti c route of PAN-based carbon fiber, more easily realizes the serialization of high heat-conductive carbon fiber and produces.
In the present invention, the main purpose of polyimides stabilisation is that to make the linear polymeric crosslinking curing of polyimides be three-dimensional polymeric molecule, makes it melting doubling phenomena can not occur in follow-up heat treatment process, has a strong impact on the performance of polyimides based carbon fiber.The mode of stabilisation comprises two kinds of gaseous oxidation or liquid phase oxidations: so-called gaseous oxidation is carried out oxidation cross-linked reaction to fiber exactly under oxidizing atmosphere (such as air, oxygen etc.); Liquid phase oxidation is carried out cross-linking and curing reaction exactly under strong oxidizer (red fuming nitric acid (RFNA) etc.) condition.
In the present invention, the low-temperature carbonization of polyimide fiber refers under inert atmosphere its stabilisation fiber is carried out to the heat treatment at 1000 DEG C, at this heat treatment stages, violent chemical reaction has occurred, and discharges a large amount of carbon containings, nitrogenous micromolecular material.If the small-molecule substance of these releases is overflowing too much of carbon containing class especially, the defect that makes fiber is increased, charcoal yield reduces, thereby greatly reduces the performance of polyimides based carbon fiber.Therefore necessary meticulous control technique, especially, for suppressing the excessive volatilization of little point of subclass material, need to apply certain tension force (or drawing-off) to stabilisation fiber, and carry out low-temperature carbonization under certain hyperbaric environment.
Graphitization in the present invention is in inert atmosphere, above-mentioned charing polyimide fiber to be heat-treated at 2400-3200 DEG C.Even higher for making in polyimides based carbon fiber graphite microcrystal remain unchanged along fiber axis to the degree of orientation, in graphitizing process, fiber is applied to certain tension force (drawing-off).
The present invention compared with prior art has following advantages:
With other Carbon fiber precursor as compared with polyacrylonitrile fibre or viscose, aromatic rings on the macromolecular chain of polyimide fiber substantially in same plane, therefore more easily develops into that graphite microcrystal is larger, fiber axis is to the higher high heat-conductive carbon fiber of the degree of orientation;
2. more easily realize industrial continuous production.The high heat-conductive carbon Precursors of Fibers using is at present mainly Mesophase Pitch Fibers, but its intensity extremely low (only several MPa) is highly brittle, and causes its serialization production process very loaded down with trivial details, and cost is very high, and domestic still none unit can produce so far.And the extension at break of polyimide fiber is usually above 4%, intensity is greater than 100MPa especially, therefore with reference to the syntheti c route of PAN-based carbon fiber, more easily realizes the serialization of high heat-conductive carbon fiber and produces.
Detailed description of the invention
Specific embodiment will be provided below, and the present invention is described in detail, but the invention is not restricted to following examples.The same document of thermal conductivity method of testing (< Journal of Inorganic Materials >, 2010,25 (9) 989-993) of polyimides based carbon fiber.
Embodiment 1
Select imide group be structural formula 1 the polyimide fiber of macromolecular chain composition, its extension at break is greater than 4%(as being 7-8%), intensity is greater than 100Mpa(as being 150-200Mpa), the axial preferred orientation degree of its macromolecular chain is greater than 60%(as being 70-80% simultaneously), these fiber two ends are fixed to (being that drawing-off is 0), be placed in heat-treatment furnace and carry out gas phase thermostabilization, under air atmosphere, speed with 5 DEG C/min clock rises to 350 DEG C by room temperature, then rise to 500 DEG C with the heating rate of 1 DEG C/min by 350 DEG C again, stop 30min; Then stabilisation fiber is carried out in the situation that draw ratio is 0 to low-temperature carbonization processing, under High Purity Nitrogen atmosphere, pressure 0.1005MPa, rises to 500 DEG C with 10 DEG C/min, then rises to 800 DEG C with the heating rate of 2 DEG C/min, insulation 30min.After cooling, fiber two ends are fixed, be placed in graphitizing furnace, under high-purity argon atmosphere, carry out graphitization processing (2600 DEG C, constant temperature 30min).At this moment the thermal conductivity of resulting materials is 136Wm
-1k
-1, density is 1.90g/cm
3.
Embodiment 2
Get the polyimide fiber meeting the demands in embodiment 1, other condition is identical with embodiment 1, just graphitization temperature is increased to 3200 DEG C, and the thermal conductivity of resulting materials reaches 391Wm
-1k
-1, density is 1.96g/cm
3.
Embodiment 3
Get the polyimide fiber meeting the demands in embodiment 1, other condition is identical with embodiment 1, but in stabilization procedures, applies 10% drawing-off, and graphitization temperature rises to 3000 DEG C simultaneously, and the thermal conductivity of resulting materials is 405Wm
-1k
-1, density is 2.05g/cm
3.
Embodiment 4
Get the polyimide fiber meeting the demands in embodiment 1, other condition is identical with embodiment 1, but in stabilization procedures, applies 10% drawing-off, then under 4% draw ratio and 4MPa pressure, carries out low-temperature carbonization, graphitization temperature rises to 3000 DEG C simultaneously, and the thermal conductivity of resulting materials is 589Wm
-1k
-1, density is 2.14g/cm
3.
Comparative example 1
Get the polyimide fiber meeting the demands in embodiment 1, other condition is identical with embodiment 1, just will in gas phase stabilization procedures, change 5 DEG C/min into by 350 DEG C of heating rates that rise to 500 DEG C, stabilisation fiber after treatment is molten and phenomenon is comparatively serious, after low-temperature carbonization, fiber is highly brittle, and is difficult to measure.
Embodiment 5
Get the polyimide fiber meeting the demands in embodiment 1, the red fuming nitric acid (RFNA) of putting into boiling carries out liquid stable, and the time is 20min.After taking-up, clean and be dried with distilled water.Then carry out low-temperature carbonization and high temperature graphitization processing, treatment conditions are with embodiment 1, and wherein graphitization temperature rises to 3000 DEG C, and the thermal conductivity of resulting materials is 255Wm
-1k
-1, density is 1.95g/cm
3.
Embodiment 6
Get the polyimide fiber meeting the demands in embodiment 1, the red fuming nitric acid (RFNA) of putting into boiling carries out liquid stable, and the time is 20min.After taking-up, clean and be dried with distilled water.Then this fiber is carried out in the situation that draw ratio is 0 to low-temperature carbonization processing, under High Purity Nitrogen atmosphere, pressure is 4MPa, rises to 500 DEG C with 10 DEG C/min, then rises to 800 DEG C with the heating rate of 2 DEG C/min.After cooling, fiber two ends are fixed, be placed in graphitizing furnace, under high-purity argon atmosphere, carry out graphitization processing (3000 DEG C, constant temperature 30min).At this moment the thermal conductivity of resulting materials is 436Wm
-1k
-1, density is 2.0g/cm
3.
Embodiment 7
Get the polyimide fiber meeting the demands in embodiment 1, the red fuming nitric acid (RFNA) of putting into boiling carries out liquid stable, and the time is 20min.After taking-up, clean and be dried with distilled water.Then this fiber is carried out in the situation that draw ratio is 4% to low-temperature carbonization processing, under High Purity Nitrogen atmosphere, pressure is 4MPa, rises to 500 DEG C with 10 DEG C/min, then rises to 1000 DEG C with the heating rate of 2 DEG C/min.After cooling, fiber two ends are fixed, be placed in graphitizing furnace, under high-purity argon atmosphere, carry out graphitization processing (3000 DEG C, constant temperature 30min).At this moment the thermal conductivity of resulting materials is 503Wm
-1k
-1, density is 2.1g/cm
3.
Comparative example 2
Get the polyimide fiber meeting the demands in embodiment 1, the red fuming nitric acid (RFNA) of putting into boiling carries out liquid stable, and the time is 60min.After taking-up, clean and be dried with distilled water, now find that fiber is more crisp.Then this fiber is carried out in the situation that draw ratio is 0 to low-temperature carbonization processing, under High Purity Nitrogen atmosphere, pressure is 4MPa, rises to 500 DEG C with 10 DEG C/min, then rises to 1000 DEG C with the heating rate of 2 DEG C/min.After taking out, find the fracture of fiber great majority, cannot obtain high heat-conductive carbon fiber.
Claims (2)
1. a method of preparing high heat conduction polyimides based carbon fiber, is characterized in that, comprises the following steps: first polyimide fiber is carried out to gas phase or liquid stable processing, make its polyimides macromolecular chain crosslinking curing; Then stabilisation fiber is carried out in nitrogen atmosphere to the charing under low temperature constraints, finally carry out high temperature graphitization processing;
Polyimide fiber described above is linear polymeric material, and wherein imide group is structural formula 1, and macromolecular chain is along fiber axis to having preferred orientation;
Described polyimide fiber extension at break is greater than 4%, intensity is greater than 100MPa, and the axial preferred orientation degree of its macromolecular chain is higher than 60% simultaneously; Described gas phase stabilisation condition: draw ratio is 0-15%, under air atmosphere or oxygen atmosphere, rises to 300-450 DEG C with the speed of 3-10 DEG C/min by room temperature, then rises to 450-550 DEG C with the heating rate of 0.5-2 DEG C/min again, stops 1-60min; Described liquid stable condition: liquid phase oxidation medium is the red fuming nitric acid (RFNA) under boiling condition, the processing time is 5-40min, polyimide fiber after treatment need be cleaned and be dried with distilled water; Described low-temperature carbonization condition: draw ratio is 0-6%, high pure nitrogen atmosphere, pressure 0.1-6MPa, rises to 500 DEG C with 5-20 DEG C/min, then rises to 800-1200 DEG C with the heating rate of 1-5 DEG C/min, and the time of staying is 1-60min; Described high temperature graphitization condition: draw ratio is 0-4%, high-purity argon atmosphere, temperature is 2400-3200 DEG C, the time of staying is 1-60min.
2. according to the method for claim 1, it is characterized in that, the processing time is 8-30min.
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| CN105483909A (en) * | 2014-09-20 | 2016-04-13 | 四川鑫达企业集团有限公司 | Advanced composite material carbon fiber heating fabric |
| CN104651979B (en) * | 2015-03-17 | 2017-09-01 | 威海拓展纤维有限公司 | The method for preparing high-strength middle model carbon fiber |
| CN107059161A (en) * | 2017-04-14 | 2017-08-18 | 江苏先诺新材料科技有限公司 | A kind of polyimide-based graphite fibre and its preparation method and application |
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