CN105696116A - Preparation method of novel high-heat conduction carbon fibers - Google Patents
Preparation method of novel high-heat conduction carbon fibers Download PDFInfo
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- CN105696116A CN105696116A CN201410677637.4A CN201410677637A CN105696116A CN 105696116 A CN105696116 A CN 105696116A CN 201410677637 A CN201410677637 A CN 201410677637A CN 105696116 A CN105696116 A CN 105696116A
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Abstract
The invention relates to a preparation method of novel high-heat conduction carbon fibers, and belongs to the technical field of preparation of functional carbon fibers. The method comprises the following steps: preparing polyimide fibers through a two-step technology; and charring the polyimide fibers under the following low-temperature constraint conditions: the drafting strength is 0.01-0.5MPa, inert atmosphere is adopted to protect, the heating rate is 1-10DEG C/min, the final charring temperature is 800-1500DEG C, and a final temperature is kept for 20-60min, in order to obtain polyimide-based carbon fibers; and graphitizing the obtained carbon fibers at a high temperature (of 2000-3200DEG C) under the protection of the inert atmosphere at a heating rate of 10-20DEG C/min in order to obtain polyimide-based graphite fibers. The graphite fibers with high crystallization degree, high graphitization degree and high heat conductivity can be obtained through the method.
Description
Technical field
The preparation method that the present invention relates to a kind of Carbon fibe being presoma with polyimides, the preparation method particularly relating to a kind of high heat conductivity carbon fiber。
Background technology
Carbon fibe has light specific gravity, high specific strength, high ratio modulus, corrosion-resistant, high temperature resistant, radioprotective, thermal shock resistance and excellent conductive performance, it is typical high-performance fiber, has had in fields such as ocean engineering, novel building, space flight and aviation, sports goods, new forms of energy, ocean development, microelectronics and be widely applied。The kind of current Carbon fibe mainly includes polyacrylonitrile (PAN) based carbon fiber, pitch based carbon fiber, rayon-based carbon fiber, and wherein, what most study, industrialization degree were the highest is polyacrylonitrile-radical and pitch based carbon fiber。
Along with the fast development of Aero-Space science and technology, in aircraft, the electronic unit of heat control system is due to the high power operating substantial amounts of warm of generation, and these heats need directed efficiently in time derivation。Presently used Heat Conduction Material such as high temperature alloy, ceramic matric composite cannot concurrently reach instructions for use in proportion, high temperature resistant, thermal conductivity, thermal coefficient of expansion and thermal shock resistance etc., and therefore its application is somewhat limited。Graphite material is light weight not only, and mechanical behavior under high temperature and thermal shock resistance are excellent, also have high heat-conductive characteristic, along graphite flake layer direction heat conductivity in theory up to 2500W m-1·K-1。Current high conductive graphite fiber is mainly prepared by mesophase pitch, and the K1100 type Mesophase Pitch-based Carbon Fibers thermal conductivity that Amoco company of the U.S. produces is up to 1100W m-1·K-1。But the refining difficulty of its presoma mesophase pitch, spinning equipment requires precision, and as-spun fibre mechanical property is non-normally low, causes subsequent heat treatment complex process, limits extensive preparation and the application of high heat conduction Mesophase Pitch-based Carbon Fibers。
Containing the aromatic structure that a large amount of flatnesses are high, the degree of orientation is high in polyimides (PI) structure, PI thin film can prepare thermal conductivity up to 1800W m through carbonization, graphitization processing in an inert atmosphere-1·K-1Graphite material。Compared to the thin-film material of two dimension, PI fiber has big advantage in orientation。Someone measures PI foundation stone ink film and the electrical conductivity of PAN base graphite fibre, it has been found that PI graphite film electrical conductivity relatively PAN base graphite fibre exceeds an order of magnitude。Therefore it is reasonable to infer that PI graphite fiberization more likely obtains high heat conductance after processing。Current polyimide fiber preparation method mainly includes dry spinning, wet spinning, wet-dry change, melt spinning, electrostatic spinning, and wherein wet method and dry-wet spinning are most widely used。This patent adopts dry-wet spinning technique, prepares PI fiber, then passes through the PI base graphite fibre of carbonization, graphitization processing acquisition high-crystallinity, high heat conduction。
Summary of the invention
The preparation method that it is an object of the invention to provide a kind of novel i.e. polyimide-based high heat conductivity carbon fiber。
The preparation of polyimide fiber mainly adopts two-step method: the first step is to carry out solution (low temperature) polycondensation by having the dianhydride of aromatic structure and diamidogen in polar non-solute (such as DMAc, DMF, NMP), obtain polyamic acid (PAA) solution, be then passed through wet method or dry-wet spinning obtains PAA fiber。Second step is that through chemical imidization or thermal cyclization, PAA fiber is obtained polyimide fiber。
With polyimide fiber for presoma, in an inert atmosphere, process through continuous high temperature, it is thus achieved that there is the graphite fibre of high-crystallinity, high-orientation, high-termal conductivity。
The method preparing polyimides based carbon fiber, it is characterised in that comprise the following steps:
A: adopt diamidogen and dianhydride low-temperature polycondensation to obtain polyamic acid solution, prepare polyamic acid as-spun fibre through dry-wet spinning technique, adopts hot-imide method to obtain polyimide fiber。
B: the polyimide fiber obtained by step A carbonization under low temperature constraints, inert atmosphere protection, terminates rear natural cooling, namely obtains polyimides based carbon fiber。
C: the Carbon fibe obtained by step B carries out graphitization processing, inert atmosphere protection in graphitizing furnace, it is thus achieved that high-crystallinity, high-orientation, high heat conduction graphite fibre。
Wherein, in step A, polyamic acid fiber adopts dry-wet spinning technique, and coagulating bath can be one or more mixture therein such as water, ethanol, acetone, ethylene glycol, DMF, DMAc, DMSO etc.。This step adopts the mixing bath of second alcohol and water to be coagulating bath。
Polyimide fiber is fixed in vacuum tube furnace by step B carbonization, heating rate 1～10oC/min, heat treatment temperature 800～1500oC, inert atmosphere protection, stop 20～60min in the temperature set, after terminating, naturally cool to room temperature。In carbonization process, maintaining the fabric in tension, the drawing-off intensity that fiber is subject to is 0.01～0.5MPa。
Carbon fibe is placed in graphitizing furnace by step C, heating rate 10～20oC/min, heat treatment temperature 2000～3200oC, inert atmosphere protection, stop 20～60min at design temperature, after terminating, naturally cool to room temperature。
The present invention compared with prior art has the advantage that
1. the present invention uses polyimides as presoma, develops a kind of new type polyimide based carbon fiber。
2. to have good compactness, defect few for the polyimides based carbon fiber prepared by the present invention, and in carbonization process, fiber is applied certain drawing-off, drastically increasing fibre orientation, the polyimides based carbon fiber therefore obtained has higher conductive performance。
3. polyimides based carbon fiber preparation technology provided by the invention is simple to operate, it is easy to accurately control, it is easier to continuous prodution。Current high heat conductivity carbon fiber is mainly prepared by mesophase pitch, but due to the refining difficulty of mesophase pitch, and the as-spun fibre intensity that melt spinning obtains is extremely low, is highly brittle, cause complex treatment process thereafter, so that the preparation difficulty of high heat conduction Mesophase Pitch-based Carbon Fibers is big, cost is high。And polyimide fiber elongation at break is usually above 4%, intensity, more than 100MPa, is therefore easier to realize the continuous prodution of high heat conduction polyimides based carbon fiber。
4. polyimide molecule structure contains the aromatic structure that a large amount of flatnesses are high, the degree of orientation is high, therefore drastically increases polyimide fiber aromatisation efficiency in stabilization procedures。Polyimide precursor only sloughs hydrone in the process of hot-imide simultaneously, and change in volume is little, therefore that the impact of fiber overall structure is little, decreases the adverse effect to end product。
5. the hexagonal net surface structure of graphite fibre after continuous high temperature graphitization processing of polyimides based carbon fiber prepared by the present invention is more perfect, and graphite microcrystal size increases, degree of orientation height improves, and has excellent conductive performance。
Accompanying drawing explanation
Fig. 1 is the preparation flow schematic diagram that the present invention prepares polyimides based carbon fiber。
Fig. 2 is prepared polyimides based carbon fiber electron scanning micrograph。
Fig. 3 is the polyimides based carbon fiber conductive performance prepared at different heat treatment temperature in embodiment。
Fig. 4 is the polyimides based carbon fiber mechanical property prepared at different heat treatment temperature in embodiment。
Detailed description of the invention
The present invention is described in detail to provide below specific embodiment, but the invention is not restricted to following example。
Embodiment 1
A: obtain polyamic acid solution by diamidogen and dianhydride low-temperature polycondensation, prepare polyamic acid fiber through dry-wet spinning technique, then adopts hot acid imide method that polyamic acid fiber is transformed into polyimide fiber, hot-imide program setting: heating rate 5oC/min, respectively 100,200,300oC respectively stops 60min。
B: the polyimide fiber obtained by step A is fixed in vacuum tube furnace, and apply 0.1MPa drawing-off intensity along its axial direction, make fiber be in tightening tension state in carbonization process。In high-purity N2Protection under, with 3oC/min heating rate is warmed up to 800oC, and stop 60min at this temperature。Then natural cooling, namely obtains polyimides based carbon fiber。The material thermal conductivity now obtained is 4.53W m-1·K-1, hot strength 745.94MPa。
Embodiment 2
Example 1 meets the polyimide fiber required, other condition is identical with embodiment 1, simply carbonization temperature is brought up to 1200oC, the thermal conductivity of obtained material reaches 44.81W m-1·K-1, hot strength 924.42MPa。
Embodiment 3
Example 1 meets the polyimide fiber required, other condition is identical with embodiment 1, and carbonization temperature is brought up to 1500oC, the thermal conductivity of obtained material is 55.97W m-1·K-1, hot strength 533.05MPa。
Embodiment 4
Example 1 meets the polyimide fiber required, other condition is identical with embodiment 1, but fiber two ends do not apply drawing-off in carbonization process, and the thermal conductivity of obtained material reaches 4.26W m-1·K-1, hot strength 539.26MPa。
Embodiment 5
Example 1 meets the polyimide fiber required, other condition is identical with embodiment 1, but fiber keeps drawing-off intensity to be 0.5MPa in carbonization process, and the thermal conductivity of obtained material is 5.85W m-1·K-1, hot strength 842.15MPa。
Embodiment 6
Example 1 meets the polyimide fiber required, other condition is identical with embodiment 1, is simply 10 by the heating rate in step BoC/min, the thermal conductivity of obtained material reaches 3.98W m-1·K-1, intensity 576.47MPa。
Embodiment 7
A: obtain polyamic acid solution by diamidogen and dianhydride low-temperature polycondensation, prepare polyamic acid fiber through dry-wet spinning technique, then adopts hot acid imide method that polyamic acid fiber is transformed into polyimide fiber。
B: the polyimide fiber obtained by step A is fixed in vacuum tube furnace, and apply 0.1MPa drawing-off intensity along its axial direction, make fiber be in tightening tension state in carbonization process。Under high pure nitrogen is protected, with 3oC/min heating rate is warmed up to 1200oC, and keep 60min at this temperature。Then natural cooling, namely obtains polyimides based carbon fiber。
C: the Carbon fibe obtained by step B is placed in graphitizing furnace, with 10oC/min ramp is to 2000oC, high-purity argon gas is protected, and stops 60min in this temperature。Then natural cooling, namely obtains polyimide-based graphite fibre。The thermal conductivity of resulting materials is 76.75W m-1·K-1, hot strength is 438.80MPa。
Embodiment 8
Example 7 meets the polyimides based carbon fiber required, other condition is identical with embodiment 7, simply graphitization temperature is brought up to 2800oC, the thermal conductivity of obtained material reaches 228.44W m-1·K-1, hot strength is 164.26MPa。
Embodiment 9
Example 8 meets the polyimides based carbon fiber required, other condition is identical with embodiment 8, simply graphitization temperature is brought up to 3200oC, the thermal conductivity of obtained material reaches 548.57W m-1·K-1, hot strength is 124.39MPa。
Below presently preferred embodiments of the present invention has been illustrated, but the present invention is not limited in described embodiment, those of ordinary skill in the art it may also be made that under the premise without prejudice to spirit of the present invention all equal modification or replacement, these equal modification or replacement are all contained in the application claim limited range。
Claims (6)
1. the preparation method of a novel high heat conduction polyimides based carbon fiber, it is characterised in that comprise the following steps:
Polyimide fiber is prepared initially with two-step method; then the polyimide fiber carbonization under low temperature constraints that will obtain; inert gas shielding; natural cooling after end; namely polyimides based carbon fiber is obtained; finally polyimides based carbon fiber is carried out graphitization processing, inert gas shielding, it is thus achieved that high-crystallinity, high heat conduction graphite fibre。
2. according to the method for claim 1, it is characterized in that, polyimide fiber preparation adopts two-step method: the first step will have dianhydride and the diamidogen low-temperature polycondensation of aromatic structure, select polar non-solute (such as DMAc, DMF, NMP), obtain polyamic acid (PAA) solution, it is then passed through wet method or dry-wet spinning obtains PAA as-spun fibre, second step: PAA as-spun fibre is processed through hot-imide and obtains polyimide fiber。
3. according to the method for claim 1, it is characterised in that described polyimide fiber elongation at break is more than 10%, and hot strength is more than 150MPa, and macromolecular chain axial preferred orientation degree is higher than 70% simultaneously。
4. according to the method for claim 1, it is characterised in that described low-temperature carbonization condition: heating rate 1～10oC/min, heat treatment temperature 800～1500oC, stops 20～60min, high-purity N in the temperature set2Protection。
5. according to the method for claim 1, it is characterised in that described high temperature graphitization condition: heating rate 10～20oC/min, heat treatment temperature 2000～3200oC, stops 20～60min in the temperature set, and high-purity Ar is protected。
6. according to the method for claim 1, it is characterised in that in low temperature constraint carbonization process, the drawing-off intensity that fiber is subject to is 0.01～0.5MPa。
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN108726505A (en) * | 2018-07-06 | 2018-11-02 | 江西克莱威纳米碳材料有限公司 | A kind of carbon nanotube heat conduction film and its manufacturing method |
| CN109056102A (en) * | 2018-08-13 | 2018-12-21 | 长春高琦聚酰亚胺材料有限公司 | A kind of black system polyimide nano-fiber filament yarn and its mass preparation method |
| CN113233453A (en) * | 2021-06-04 | 2021-08-10 | 四川大学 | High-electric-conductivity heat-conduction graphite material and preparation method thereof |
| KR20220094616A (en) * | 2020-12-29 | 2022-07-06 | 주식회사 디쏠 | Polyimide-based carbon fibers and graphite fibers and manufacturing methods thereof |
| WO2023080715A1 (en) * | 2021-11-04 | 2023-05-11 | 한국과학기술연구원 | Method for preparing carbon composite fiber, and carbon nanofiber |
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2014
- 2014-11-24 CN CN201410677637.4A patent/CN105696116A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN108726505A (en) * | 2018-07-06 | 2018-11-02 | 江西克莱威纳米碳材料有限公司 | A kind of carbon nanotube heat conduction film and its manufacturing method |
| CN109056102A (en) * | 2018-08-13 | 2018-12-21 | 长春高琦聚酰亚胺材料有限公司 | A kind of black system polyimide nano-fiber filament yarn and its mass preparation method |
| KR20220094616A (en) * | 2020-12-29 | 2022-07-06 | 주식회사 디쏠 | Polyimide-based carbon fibers and graphite fibers and manufacturing methods thereof |
| KR102531748B1 (en) | 2020-12-29 | 2023-05-11 | 주식회사 디쏠 | Polyimide-based carbon fibers and graphite fibers and manufacturing methods thereof |
| CN113233453A (en) * | 2021-06-04 | 2021-08-10 | 四川大学 | High-electric-conductivity heat-conduction graphite material and preparation method thereof |
| CN113233453B (en) * | 2021-06-04 | 2022-12-02 | 四川大学 | High-electric-conductivity heat-conduction graphite material and preparation method thereof |
| WO2023080715A1 (en) * | 2021-11-04 | 2023-05-11 | 한국과학기술연구원 | Method for preparing carbon composite fiber, and carbon nanofiber |
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