CN102766990A - Preparation method of high heat conductivity carbon fiber - Google Patents
Preparation method of high heat conductivity carbon fiber Download PDFInfo
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- CN102766990A CN102766990A CN2012102287276A CN201210228727A CN102766990A CN 102766990 A CN102766990 A CN 102766990A CN 2012102287276 A CN2012102287276 A CN 2012102287276A CN 201210228727 A CN201210228727 A CN 201210228727A CN 102766990 A CN102766990 A CN 102766990A
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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 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 high heat conduction charcoal fiber preparation method, belong to the preparing technical field of charcoal fiber.
Background technology
Along with the raising of quality of the life, people to the lightweight of portable high-end entertainment electronics appliances, miniaturization (approaching) require increasingly high; Simultaneously, also require the performance of these electronic equipments increasingly high, function is more and more.The requirement of this two aspect impels the critical piece (like CPU etc.) of these electronic equipments integrated degree is increasingly high, speed is more and more faster and volume is more and more littler; Thereby in running, produced more heat; Cause machine overheated; It is not good that the user of these equipment is experienced, and frequently crashes even damage.For each parts operation of making these equipment is normal, efficient, these heats must directedly timely be derived.
Novel hypersonic vehicle need stand low-density hot-fluid (1MW/m in long-time (more than the 1000S) in the process under arms
2Magnitude) lasting heating, it is very high always to add heat.Simultaneously, the complicated profile of this aircraft also causes many privileged sites to stand stronger heating relatively, makes the temperature of its large tracts of land 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 advances the laboratory to propose the notion of heat management for this reason; In order to the hot-fluid of Comprehensive Control different parts, make the high-temperature region hot-fluid to the low-temperature space transmission, thereby reduce the thermo-lag difficulty in high-temperature region.At present used Heat Conduction Material such as Ni based high-temperature alloy, ceramic matric composite etc. are difficult to reach simultaneously instructions for use at aspects such as proportion, high temperature resistant, directional heat conductance, thermal coefficient of expansion and thermal shock resistances, use and receive certain limitation.Therefore press for a kind of novel directed highly heat-conductive material of development to satisfy the flourish requirement of aerospace science and technology.
Graphite material not only has lower density (2.26g/cm
3About) and excellent mechanical behavior under high temperature, also have excellent thermal shock resistance and high thermal conduction characteristic, be to satisfy a kind of high heat conduction management material that above-mentioned field requires.The high thermal conduction characteristic of graphite material comes from the high thermal conductivity coefficient that has along the graphite flake layer direction of the netted structural group one-tenth of carbon hexagonal (can reach 2500Wm in theory
-1K
-1), and perpendicular to the thermal conductivity of graphite flake layer direction 6Wm only
-1K
-1Therefore in the preparation process of high-heat conductivity graphite material, graphite flake layer is arranged along same direction, and in use maximized favourable factors and minimized unfavourable ones, heat transmitted in the direction through suitable design.Most graphite flake layers along fiber axis to the high-performance continuous graphite fiber of arranging according to qualifications (GF), at fiber axis to having high thermal.Can arrange (or braiding) and be combined into the high heat conduction based composite material of carbon of needed orientation through suitable design.
The high heat conduction charcoal fiber presoma that uses at present mainly is the mesophase pitch fiber, but the intensity of this kind fiber extremely low (only a few MPa) is highly brittle, and causes its serialization production process very loaded down with trivial details, and cost is very high, and domestic so far still none tame unit can produce.Therefore seeking one differs from the high heat conduction GF of former research and development path of preparing and has very important significance.
The researcher finds to have polyimides (PI) polymeric membrane of high-orientation in the process of the high oriented graphite of preparation, warp pressurization charing, graphitization can make the graphite film of high crystalline and high-orientation in inert atmosphere.The height-oriented PI films of employings such as Japan scientist Murakami are raw material, through cutting, range upon range of, 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 defective in the film, need apply high pressure and heating rate very slowly, the preparation condition harshness.This method is difficult to prepare bulk sample and mass production, and its application has received than limitations.If polyimides is spun into fiber, high heat conduction GF is processed in heat treatment to fiber again, with the range of application of expanding it greatly, will have broad application prospects.And the PI fiber is as high polymer fibre, and its extension at break is usually above 10%, and intensity very easily realizes the serialization production of high heat conduction charcoal fiber greater than 100MPa.
Owing to receive than high draft in the spinning moulding process, its macromolecular chain is mostly along the fiber axis preferred orientation in the preparation process for the PI fiber.Therefore, compare in the orientation of PI strand in fiber and the film, higher along fiber axis to the degree of orientation, arrange more regular; While, the PI macromolecular chain was similar to the long band of a rigidity owing to contain more aromatic rings on the main chain, and aromatic rings is distributed on long wide of being with mostly.The arrangement mode of this aromatic rings is similar to the mesophase pitch fiber very much.And the molecular weight of PI is high far beyond mesophase pitch, and its strand along fiber axial height preferred orientation also is longer than mesophase pitch.This molecular structure possibly generate that size is bigger, defective graphite lattice still less.
Summary of the invention
The object of the invention just provide a kind of novel be polyimide-based high heat conduction charcoal fiber preparation method, correlative study also is not shown in any public reported at present.
The present invention will be with reference to the preparation method of high-performance PAN based carbon fiber and high heat conduction MP base GF; Through the PI fiber is carried out stabilisation, charing, graphitization processing; And in heat treatment process, apply the pressure in the high orientation of drawing-off (tension force) the replacement PI film carbonization process, obtain to have the high heat conduction GF of high-crystallinity, high-orientation.
The present invention prepares the method for high heat conduction polyimides based carbon fiber, it is characterized in that, may further comprise the steps: at first polyimide fiber is carried out gas phase or liquid stable processing, make its polyimides macromolecular chain crosslinking curing; Then the stabilisation fiber is carried out the charing under the low temperature constraints in nitrogen atmosphere, carry out high temperature graphitization at last and handle.
Above-mentioned described polyimide fiber is the linear polymeric material, and wherein imide group is a structural formula 1, these macromolecular chains along fiber axis to have the height preferred orientation.
Structural formula 1
The preferred extension at break of above-mentioned described polyimide fiber greater than 4%, intensity is greater than 100MPa, the axial preferred orientation degree of its macromolecular chain is higher than 60% simultaneously.
Above-mentioned described gas phase stabilisation condition: draw ratio is 0-15%, and air atmosphere down or oxygen atmosphere rises to 300-450 ℃ with the speed of 3-10 ℃/min by room temperature, rises to 450-550 ℃ with the heating rate of 0.5-2 ℃/min again then, stops 1-60min.(two sections above-mentioned heat treatment processes are not 450 ℃ simultaneously)
Above-mentioned described liquid stable condition: the liquid phase oxidation medium is the red fuming nitric acid (RFNA) (mass concentration 68%) under the boiling condition, and the processing time is 5-40min (optimal time is 8-30min), and the polyimide fiber after the processing needs to clean and drying with distilled water.
Above-mentioned described low-temperature carbonization condition: draw ratio is 0-6%, high pure nitrogen atmosphere, and pressure 0.1-6MPa rises to 500 ℃ with 5-20 ℃/min, and the heating rate with 1-5 ℃/min rises to 800-1200 ℃ then, and the time of staying is 1-60min.
Above-mentioned described high temperature graphitization condition: draw ratio is 0-4%, and high-purity argon atmosphere, temperature are 2400-3200 ℃, and the time of staying is 1-60min.
Above-mentioned high pure nitrogen atmosphere preferably is not less than 99.9% nitrogen.
The polyimide fiber that the present invention is used, those skilled in the art, the method for preparing fiber through routine can prepare.As adopt following method.
One-step method spinning polyimide fiber: two kinds of monomers of dianhydride and diamines are heated to 150 ℃ ~ 250 ℃ and acquisition polyimides in high boiling solvent (like phenols).With the polyimide solution is spinning slurry, and wet method or dried wet method spinning polyimide fiber, fiber behind the removal solvent, carry out hot-stretch and handle (300 ℃ ~ 500 ℃) after preliminary the stretching, can obtain polyimide fiber.
Two step method spinning polyimide fiber: the first step is that dianhydride and diamines are carried out solution (low temperature) polycondensation in aprotic polar solvent (like dimethyl formamide), obtains polyamic acid solution, through wet method or dried wet method spray silk, obtains the polyamic acid fiber.Second the step be with the polyamic acid fiber through chemical cyclisation or thermal cyclization, obtain polyimide fiber.The stretching process of fiber can carry out in the first step, also can in the process of the second step imidizate, carry out, and perhaps each step is all carried out certain stretching.
Above-mentioned used dianhydride and diamines are the dianhydride and the diamines of the imide group that can obtain structural formula 1.
The main purpose of polyimides stabilisation is that to make the linear polymeric crosslinking curing of polyimides be three-dimensional polymeric molecule among the present invention, makes it fusion doubling phenomenon can not take place 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.
The low-temperature carbonization of polyimide fiber is meant under inert atmosphere its stabilisation fiber is carried out the heat treatment under 1000 ℃ among the present invention, at this heat treatment stages violent chemical reaction has taken place, 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 defective that makes fiber is increased, charcoal yield reduces, thereby reduces the performance of polyimides based carbon fiber greatly.Therefore necessary meticulous control process especially for suppressing the excessive volatilization of micromolecule class material, need apply certain force of strain (or drawing-off) to the stabilisation fiber, and under certain hyperbaric environment, carry out low-temperature carbonization.
Graphitization among the present invention is in inert atmosphere, above-mentioned charing polyimide fiber to be heat-treated under 2400-3200 ℃.For graphite microcrystal is remained unchanged even higher to the degree of orientation along fiber axis, in graphitizing process, fiber has been applied certain force of strain (drawing-off).
The present invention compared with prior art has advantage:
1. compare with other charcoal fiber presoma such as polyacrylonitrile fibre or viscose; Therefore aromatic rings on the macromolecular chain of polyimide fiber is prone to more develop into that graphite microcrystal is bigger, fiber axis is to the higher high heat conduction charcoal fiber of the degree of orientation basically in same plane;
2. more be prone to realize industrial continuous production.The high heat conduction charcoal fiber presoma that uses at present mainly is the mesophase pitch fiber, but its intensity extremely low (only a few MPa) is highly brittle, and causes its serialization production process very loaded down with trivial details, and cost is very high, and domestic so far still none tame unit can produce.And the extension at break of polyimide fiber is usually above 4%, and therefore intensity with reference to the preparation route of polyacrylonitrile charcoal fiber, more be prone to realize the serialization production of high heat conduction charcoal fiber especially greater than 100MPa.
The main purpose of polyimides stabilisation is that to make the linear polymeric crosslinking curing of polyimides be three-dimensional polymeric molecule among the present invention, makes it fusion doubling phenomenon can not take place 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.
The low-temperature carbonization of polyimide fiber is meant under inert atmosphere its stabilisation fiber is carried out the heat treatment under 1000 ℃ among the present invention, at this heat treatment stages violent chemical reaction has taken place, 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 defective that makes fiber is increased, charcoal yield reduces, thereby reduces the performance of polyimides based carbon fiber greatly.Therefore necessary meticulous control process especially for suppressing the excessive volatilization of micromolecule class material, need apply certain force of strain (or drawing-off) to the stabilisation fiber, and under certain hyperbaric environment, carry out low-temperature carbonization.
Graphitization among the present invention is in inert atmosphere, above-mentioned charing polyimide fiber to be heat-treated under 2400-3200 ℃.For graphite microcrystal is remained unchanged even higher to the degree of orientation along fiber axis, in graphitizing process, fiber has been applied certain force of strain (drawing-off).
The present invention compared with prior art has advantage:
1. compare with other charcoal fiber presoma such as polyacrylonitrile fibre or viscose; Therefore aromatic rings on the macromolecular chain of polyimide fiber is prone to more develop into that graphite microcrystal is bigger, fiber axis is to the higher high heat conduction charcoal fiber of the degree of orientation basically in same plane;
2. more be prone to realize industrial continuous production.The high heat conduction charcoal fiber presoma that uses at present mainly is the mesophase pitch fiber, but its intensity extremely low (only a few MPa) is highly brittle, and causes its serialization production process very loaded down with trivial details, and cost is very high, and domestic so far still none tame unit can produce.And the extension at break of polyimide fiber is usually above 4%, and therefore intensity with reference to the preparation route of polyacrylonitrile charcoal fiber, more be prone to realize the serialization production of high heat conduction charcoal fiber especially greater than 100MPa.
The specific embodiment
To provide specific embodiment that the present invention is elaborated below, but the invention is not restricted to following examples.The same document of thermal conductivity method of testing of polyimides based carbon fiber (< Journal of Inorganic Materials >, 2010,25 (9) 989-993).
Embodiment 1
Select for use imide group be structural formula 1 the polyimide fiber formed of macromolecular chain; Its extension at break is greater than 4% (as being 7-8%), and intensity is greater than 100Mpa (as being 150-200Mpa), and the axial preferred orientation degree of its macromolecular chain is greater than 60% (as being 70-80%) simultaneously; These fiber two ends are fixed (being that drawing-off is 0); Place heat-treatment furnace to carry out the gas phase thermostabilization, under the air atmosphere, rise to 350 ℃ by room temperature with the speed of 5 ℃/min clock; Rise to 500 ℃ with the heating rate of 1 ℃/min by 350 ℃ again then, stop 30min; Be to carry out low-temperature carbonization under 0 the situation to handle in draw ratio with the stabilisation fiber then, under the high pure nitrogen atmosphere, pressure 0.1005MPa rises to 500 ℃ with 10 ℃/min, and the heating rate with 2 ℃/min rises to 800 ℃ then, insulation 30min.After the cooling, the fiber two ends are fixed, placed in the graphitizing furnace, carry out graphitization processing (2600 ℃, constant temperature 30min) under the high-purity argon atmosphere.At this moment the thermal conductivity of gained material is 136Wm
-1K
-1, density is 1.90g/cm
3
Embodiment 2
Get the polyimide fiber that meets the demands among the embodiment 1, other condition is identical with embodiment 1, just graphitization temperature is increased to 3200 ℃, and the thermal conductivity of gained material reaches 391Wm
-1K
-1, density is 1.96g/cm
3
Embodiment 3
Get the polyimide fiber that meets the demands among the embodiment 1, other condition is identical with embodiment 1, but in stabilization procedures, applies 10% drawing-off, and graphitization temperature rises to 3000 ℃ simultaneously, and the thermal conductivity of gained material is 405Wm
-1K
-1, density is 2.05g/cm
3
Embodiment 4
Get the polyimide fiber that meets the demands among the embodiment 1; Other condition is identical with embodiment 1, but in stabilization procedures, applies 10% drawing-off, under 4% draw ratio and 4MPa pressure, carries out low-temperature carbonization then; Graphitization temperature rises to 3000 ℃ simultaneously, and the thermal conductivity of gained material is 589Wm
-1K
-1, density is 2.14g/cm
3
Comparative Examples 1
Get the polyimide fiber that meets the demands among the embodiment 1; Other condition is identical with embodiment 1; Just with changing 5 ℃/min into by 350 ℃ of heating rates that rise to 500 ℃ in the gas phase stabilization procedures; Stabilisation fiber after the processing is molten and phenomenon is comparatively serious, and fiber is highly brittle behind the low-temperature carbonization, is difficult to measure.
Embodiment 5
Get the polyimide fiber that meets the demands among the embodiment 1, the red fuming nitric acid (RFNA) of putting into boiling carry out liquid stableization, and the time is 20min.After the taking-up, clean and drying with distilled water.Carry out low-temperature carbonization and high temperature graphitization then and handle, treatment conditions are with embodiment 1, and wherein graphitization temperature rises to 3000 ℃, and the thermal conductivity of gained material is 255Wm
-1K
-1, density is 1.95g/cm
3
Embodiment 6
Get the polyimide fiber that meets the demands among the embodiment 1, the red fuming nitric acid (RFNA) of putting into boiling carry out liquid stableization, and the time is 20min.After the taking-up, clean and drying with distilled water.Be to carry out low-temperature carbonization under 0 the situation to handle in draw ratio with this fiber then, under the high pure nitrogen atmosphere, pressure is 4MPa, rises to 500 ℃ with 10 ℃/min, and the heating rate with 2 ℃/min rises to 800 ℃ then.After the cooling, the fiber two ends are fixed, placed in the graphitizing furnace, carry out graphitization processing (3000 ℃, constant temperature 30min) under the high-purity argon atmosphere.At this moment the thermal conductivity of gained material is 436Wm
-1K
-1, density is 2.0g/cm
3
Embodiment 7
Get the polyimide fiber that meets the demands among the embodiment 1, the red fuming nitric acid (RFNA) of putting into boiling carry out liquid stableization, and the time is 20min.After the taking-up, clean and drying with distilled water.Be to carry out low-temperature carbonization under 4% the situation to handle in draw ratio with this fiber then, under the high pure nitrogen atmosphere, pressure is 4MPa, rises to 500 ℃ with 10 ℃/min, and the heating rate with 2 ℃/min rises to 1000 ℃ then.After the cooling, the fiber two ends are fixed, placed in the graphitizing furnace, carry out graphitization processing (3000 ℃, constant temperature 30min) under the high-purity argon atmosphere.At this moment the thermal conductivity of gained material is 503Wm
-1K
-1, density is 2.1g/cm
3
Comparative Examples 2
Get the polyimide fiber that meets the demands among the embodiment 1, the red fuming nitric acid (RFNA) of putting into boiling carry out liquid stableization, and the time is 60min.After the taking-up, clean and drying with distilled water, find that fiber is more crisp this moment.Be to carry out low-temperature carbonization under 0 the situation to handle in draw ratio with this fiber then, under the high pure nitrogen atmosphere, pressure is 4MPa, rises to 500 ℃ with 10 ℃/min, and the heating rate with 2 ℃/min rises to 1000 ℃ then.Take out the back and find the fracture of fiber great majority, can't obtain high heat conduction charcoal fiber.
Claims (7)
1. a method for preparing high heat conduction polyimides based carbon fiber is characterized in that, may further comprise the steps: at first polyimide fiber is carried out gas phase or liquid stable processing, make its polyimides macromolecular chain crosslinking curing; Then the stabilisation fiber is carried out the charing under the low temperature constraints in nitrogen atmosphere, carry out high temperature graphitization at last and handle;
Above-mentioned described polyimide fiber is the linear polymeric material, and wherein imide group is a structural formula 1, macromolecular chain along fiber axis to having preferred orientation;
Structural formula 1.
2. according to the method for claim 1, it is characterized in that, described polyimide fiber extension at break greater than 4%, intensity is greater than 100MPa, the axial preferred orientation degree of its macromolecular chain is higher than 60% simultaneously.
3. according to the method for claim 1; It is characterized in that; Described gas phase stabilisation condition: draw ratio is 0-15%, and air atmosphere down or oxygen atmosphere rises to 300-450 ℃ with the speed of 3-10 ℃/min by room temperature; Rise to 450-550 ℃ with the heating rate of 0.5-2 ℃/min again then, stop 1-60min.
4. according to the method for claim 1, it is characterized in that above-mentioned described liquid stable condition: the liquid phase oxidation medium is the red fuming nitric acid (RFNA) under the boiling condition, and the processing time is 5-40min, the polyimide fiber after the processing needs to clean and drying with distilled water.
5. according to the method for claim 4, it is characterized in that the processing time is 8-30min.
6. according to the method for claim 1, it is characterized in that described low-temperature carbonization condition: draw ratio is 0-6%; High pure nitrogen atmosphere, pressure 0.1-6MPa rises to 500 ℃ with 5-20 ℃/min; Heating rate with 1-5 ℃/min rises to 800-1200 ℃ then, and the time of staying is 1-60min.
7. according to the method for claim 1, it is characterized in that described high temperature graphitization condition: draw ratio is 0-4%, and high-purity argon atmosphere, temperature are 2400-3200 ℃, and the time of staying is 1-60min.
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| CN104651979A (en) * | 2015-03-17 | 2015-05-27 | 威海拓展纤维有限公司 | Preparation method of high-strength medium-model carbon fiber |
| 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 |
| 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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| 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 |
| CN104651979A (en) * | 2015-03-17 | 2015-05-27 | 威海拓展纤维有限公司 | Preparation method of high-strength medium-model carbon fiber |
| 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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