CN108070918A - Preparing surface using polyacrylonitrile has the method for boron nitride coating carbon fiber - Google Patents
Preparing surface using polyacrylonitrile has the method for boron nitride coating carbon fiber Download PDFInfo
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- CN108070918A CN108070918A CN201611028877.7A CN201611028877A CN108070918A CN 108070918 A CN108070918 A CN 108070918A CN 201611028877 A CN201611028877 A CN 201611028877A CN 108070918 A CN108070918 A CN 108070918A
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- D06M11/80—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with boron or compounds thereof, e.g. borides
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Abstract
The invention discloses a kind of methods for having boron nitride coating carbon fiber using polyacrylonitrile preparation surface, belong to high-temperature oxidation resistant coating preparation field.The method for having boron nitride coating carbon fiber using polyacrylonitrile preparation surface of the present invention, comprises the following steps：1：Oil removing, decontamination, drying are carried out to polyacrylonitrile fibril；2：Using absolute ethyl alcohol as solvent, boric acid urea dipping solution is configured with boric acid and urea；3：The polyacrylonitrile that step 1 is obtained is put into step 2 and obtains impregnating in boric acid urea dipping solution, then dries；4：The polyacrylonitrile that step 3 is obtained, which is put into pre-oxidation furnace, to be pre-oxidized；5：The polyacrylonitrile that step 4 is obtained is put into high temperature process furnances, is heated up under protective gas atmosphere, and heat preservation is cooled to room temperature taking-up sample.The present invention can solve the problems such as other carbon fiber surface boron nitride coating preparation method temperature are high, process is complicated, of high cost, increase the high-temperature oxidation resistance of carbon fiber, improve its temperature in use.
Description
Technical field
The present invention relates to high-temperature oxidation resistant coating preparation fields, and particularly relating to a kind of utilization polyacrylonitrile preparation surface has nitrogen
Change the method for boron coat carbon fiber.
Background technology
Carbon fiber is a kind of newer, high-performance fiber materials of phosphorus content more than 92%, has light-weight, high intensity, height
A variety of excellent properties such as modulus, wear-resisting, corrosion-resistant, antifatigue, conductive, heat conduction and far infrared radiation, therefore, carbon fiber become state
The irreplaceable pillar material of anti-civilian industry.At present, polyacrylonitrile (polyacrylonitrile) fiber is oxidized, carbonizes to become and study
With the mainstream technology of production carbon fiber.But the high-temperature oxidation resistance of carbon fiber is low, temperature is higher than 400 in oxidizing atmosphere
DEG C when will start to aoxidize, when temperature higher, may cause composite materials property to decline even to fail.It is therefore, it is necessary to right
Carbon fiber is modified, it is made to remain to that the mechanical properties such as intensity, modulus is kept not reduce at high temperature.Hexagonal boron nitride has low
The excellent properties such as density, high-melting-point, high resistivity, good heat transfer and extremely low dielectric constant, in addition it is also with good
Corrosion stability and the layer structure of wear-resisting property and class graphite, so boron nitride become the preferable coating material of carbon fiber surface.
Therefore preparing boron nitride coating in carbon fiber surface increases its inoxidizability, improves the effective ways of its temperature in use.
Technology relevant with carbon fiber surface boron nitride coating is most of using carbon fiber as matrix, is improved by coating technology
The high-temperature oxidation resistance of carbon fiber, preparation method activate, using molten mainly first by carbon-fiber high-temperature calcination through pernitric acid
Liquid dip-coating and heat treatment, are finally made boron nitride coating in fiber surface.
Wei Yong mountains et al. (preparation of carbon fiber surface BN coatings and characterization [J] functional materials, 2014 (z1):76-78.)
Using boric acid as raw material, using solution dip coating, addition polyvinyl alcohol is prepared for nitrogenizing as intermediate conversion object in carbon fiber surface
Boron coating improves the antioxygenic property of carbon fiber.
Chinese patent document CN103924443A discloses a kind of preparation method of carbon fiber surface antioxidant coating.With having
Solvent removes carbon fiber surface glue-line and attached crop, coating paste is prepared using silane coupling agent as presoma, by what is obtained
Coating paste is coated on carbon fiber product surface and drying, but needs in 99.999% high-purity inert atmosphere, through 800-
1600 DEG C of high-temperature process can just obtain carbon fiber surface antioxidant coating.
Chinese patent document CN105669253A discloses a kind of method that low-temp low-pressure prepares boron nitride coating, with trichlorine
Change boron (BCl3) and ammonia (NH3) it is primary raw material, chemical vapor deposition is carried out under cryogenic, then gained sample is carried out
Boron nitride coating can be made in high-temperature heat treatment.The method finally still needs high-temperature heat treatment, and boron chloride and ammonia are all
It is than relatively hazardous gas.
In the prior art when preparing carbon fiber surface boron nitride coating, most of side using to surface treatment of carbon fibers
For method, it is necessary to first be pre-processed to carbon fiber, and activated with nitric acid, preparation process is complicated, of high cost.
The content of the invention
The technical problem to be solved in the present invention is to provide it is a kind of it is simple for process, at low cost, high-temperature oxidation resistance is excellent
Preparing surface using polyacrylonitrile has the method for boron nitride coating carbon fiber.This method energy overcome the deficiencies in the prior art, solution
Certainly existing coating process preparation temperature height, complex process, it is of high cost the problems such as, increase the antioxygenic property of carbon fiber, improve it
Temperature in use.
In order to solve the above technical problems, present invention offer technical solution is as follows：
A kind of method for having boron nitride coating carbon fiber using polyacrylonitrile preparation surface, comprises the following steps：
Step 1：Oil removing, decontamination, drying are carried out to polyacrylonitrile fibril；
Step 2：Using absolute ethyl alcohol as solvent, the boric acid for being 0.6-0.8mol/L with boric acid and urea configuration boric acid concentration is urinated
Plain dipping solution；
Step 3：The polyacrylonitrile that step 1 is obtained is put into step 2 and obtains impregnating in boric acid urea dipping solution, then dries
It is dry；
Step 4：The polyacrylonitrile that step 3 is obtained, which is put into pre-oxidation furnace, to be pre-oxidized；
Step 5：The polyacrylonitrile that step 4 is obtained is put into high temperature process furnances, is heated up under protective gas atmosphere, is protected
Temperature is cooled to room temperature taking-up sample.
Wherein, polyacrylonitrile fibril K numbers are any one in 1K, 3K, 6K, 10K in the step 1.
Further, the molar ratio of boric acid and urea is 2-5 in the step 2:1.
Better effect in order to obtain, the time impregnated in the step 3 are 1-4h.
Wherein, the Pre oxidation in the step 4 is 260-280 DEG C, and the time of pre-oxidation is 2-3h.
Preferably, the protective gas in the step 5 is nitrogen or argon gas, and heating and the rate to cool down are 2-4 DEG C/min,
Holding temperature is 800-1000 DEG C, soaking time 4-6h.
The invention has the advantages that：
The present invention provides a kind of method for having boron nitride coating carbon fiber using polyacrylonitrile preparation surface, energy of the present invention
Overcome the deficiencies in the prior art solves the shortcomings of existing coating process is complicated, of high cost, improves the high-temperature oxidation resistance of carbon fiber
Can, improve its temperature in use.
Description of the drawings
Fig. 1 is unmodified poly- the third of the method for having boron nitride coating carbon fiber using polyacrylonitrile preparation surface of the present invention
Cross-section morphology scanning electron microscopic picture after alkene nitrile precursor pre-oxidation；
The modified of method for having boron nitride coating carbon fiber using polyacrylonitrile preparation surface that Fig. 2 is the present invention gathers
Sample section topography scan electron microscopic picture after acrylonitrile precursor pre-oxidation.
Specific embodiment
The present invention provides a kind of method for having boron nitride coating carbon fiber using polyacrylonitrile preparation surface, to make this hair
Bright purpose, technical solution and effect are clearer, clear and definite, and the present invention is described in more detail below.It should be appreciated that herein
Described specific embodiment is only used to explain the present invention, is not intended to limit the present invention.
Embodiment 1
Step 1：Oil removing, decontamination, drying are carried out to polyacrylonitrile surface；
Step 2：Using absolute ethyl alcohol as solvent, boric acid and urea in molar ratio 2:1 ratio is dissolved in absolute ethyl alcohol, configuration
Boric acid concentration is 0.6mol/L, is stirred for being dispersed to uniform solution in ultrasound, then polyacrylonitrile is put into solution
Impregnate 2h；
Step 3：The modified polyacrylonitrile precursor that step 2 is obtained puts 80 DEG C of drying 0.5h in an oven, then poly- third
Alkene nitrile precursor is put into pre-oxidation furnace, is heated to 260 DEG C, is pre-oxidized 2h in air；
Step 4：Step 3 is obtained modified polyacrylonitrile oxidization fiber to be put into tube furnace, under the atmosphere of nitrogen with 2 DEG C/
The speed of min is warming up to 800 DEG C, then keeps the temperature 4h, and sample is taken out after being then cooled to room temperature with the speed of 2 DEG C/min.
Auger electron spectroscopy (AES) and FTIR spectrum (FTIR) analysis are carried out to sample, fiber surface B is measured and contains
It measures as 18.5%, N content 17%, and in 1380-1400cm-1There are stronger B-N absorption peak strengths at place.
Embodiment 2
Step 1：Oil removing, decontamination, drying are carried out to polyacrylonitrile surface；
Step 2：Using absolute ethyl alcohol as solvent, boric acid and urea in molar ratio 3:1 ratio is dissolved in absolute ethyl alcohol, configuration
Boric acid concentration is 0.7mol/L, is stirred for being dispersed to uniform solution in ultrasound, then polyacrylonitrile is put into solution
Impregnate 2h；
Step 3：The modified polyacrylonitrile precursor that step 2 is obtained puts 80 DEG C of drying 0.5h in an oven, then poly- third
Alkene nitrile precursor is put into pre-oxidation furnace, is heated to 260 DEG C, is pre-oxidized 2.5h in air；
Step 4：Step 3 is obtained modified polyacrylonitrile oxidization fiber to be put into tube furnace, under the atmosphere of nitrogen with 2 DEG C/
The speed of min is warming up to 800 DEG C, then keeps the temperature 4h, and sample is taken out after being then cooled to room temperature with the speed of 2 DEG C/min.
Auger electron spectroscopy (AES) and FTIR spectrum (FTIR) analysis are carried out to sample, fiber surface B is measured and contains
It measures as 18.9%, N content 17.4%, and in 1380-1400cm-1There are stronger B-N absorption peak strengths at place.
Embodiment 3
Step 1：Oil removing, decontamination, drying are carried out to polyacrylonitrile surface；
Step 2：Using absolute ethyl alcohol as solvent, boric acid and urea in molar ratio 3.5:1 ratio is dissolved in absolute ethyl alcohol, matches somebody with somebody
Boric acid concentration is put as 0.6mol/L, is stirred for being dispersed to uniform solution in ultrasound, polyacrylonitrile is then put into solution
Middle dipping 2h；
Step 3：The modified polyacrylonitrile precursor that step 2 is obtained puts 80 DEG C of drying 0.5h in an oven, then poly- third
Alkene nitrile precursor is put into pre-oxidation furnace, is heated to 270 DEG C, is pre-oxidized 2.5h in air；
Step 4：Step 3 is obtained modified polyacrylonitrile oxidization fiber to be put into tube furnace, under the atmosphere of nitrogen with 3 DEG C/
The speed of min is warming up to 900 DEG C, then keeps the temperature 5h, and sample is taken out after being then cooled to room temperature with the speed of 3 DEG C/min.
Auger electron spectroscopy (AES) and FTIR spectrum (FTIR) analysis are carried out to sample, fiber surface B is measured and contains
It measures as 18.6%, N content 17.2%, and in 1380-1400cm-1There are stronger B-N absorption peak strengths at place.
Embodiment 4
Step 1：Oil removing, decontamination, drying are carried out to polyacrylonitrile surface；
Step 2：Using absolute ethyl alcohol as solvent, boric acid and urea in molar ratio 4:1 ratio is dissolved in absolute ethyl alcohol, configuration
Boric acid concentration is 0.8mol/L, is stirred for being dispersed to uniform solution in ultrasound, then polyacrylonitrile is put into solution
Impregnate 2h；
Step 3：The modified polyacrylonitrile precursor that step 2 is obtained puts 80 DEG C of drying 0.5h in an oven, then poly- third
Alkene nitrile precursor is put into pre-oxidation furnace, is heated to 270 DEG C, is pre-oxidized 2.5h in air；
Step 4：Step 3 is obtained modified polyacrylonitrile oxidization fiber to be put into tube furnace, under the atmosphere of nitrogen with 3 DEG C/
The speed of min is warming up to 900 DEG C, then keeps the temperature 5h, and sample is taken out after being then cooled to room temperature with the speed of 3 DEG C/min.
Auger electron spectroscopy (AES) and FTIR spectrum (FTIR) analysis are carried out to sample, fiber surface B is measured and contains
It measures as 19.2%, N content 17.9%, and in 1380-1400cm-1There are stronger B-N absorption peak strengths at place.
Embodiment 5
Step 1：Oil removing, decontamination, drying are carried out to polyacrylonitrile surface；
Step 2：Using absolute ethyl alcohol as solvent, boric acid and urea in molar ratio 4.5:1 ratio is dissolved in absolute ethyl alcohol, matches somebody with somebody
Boric acid concentration is put as 0.7mol/L, is stirred for being dispersed to uniform solution in ultrasound, polyacrylonitrile is then put into solution
Middle dipping 2h；
Step 3：The modified polyacrylonitrile precursor that step 2 is obtained puts 80 DEG C of drying 0.5h in an oven, then poly- third
Alkene nitrile precursor is put into pre-oxidation furnace, is heated to 280 DEG C, is pre-oxidized 3h in air；
Step 4：Step 3 is obtained modified polyacrylonitrile oxidization fiber to be put into tube furnace, under the atmosphere of nitrogen with 4 DEG C/
The speed of min is warming up to 1000 DEG C, then keeps the temperature 6h, and sample is taken out after being then cooled to room temperature with the speed of 4 DEG C/min.
Auger electron spectroscopy (AES) and FTIR spectrum (FTIR) analysis are carried out to sample, fiber surface B is measured and contains
It measures as 18.6%, N content 17.3%, and in 1380-1400cm-1There are stronger B-N absorption peak strengths at place.
Embodiment 6
Step 1：Oil removing, decontamination, drying are carried out to polyacrylonitrile surface；
Step 2：Using absolute ethyl alcohol as solvent, boric acid and urea in molar ratio 5:1 ratio is dissolved in absolute ethyl alcohol, configuration
Boric acid concentration is 0.8mol/L, is stirred for being dispersed to uniform solution in ultrasound, then polyacrylonitrile is put into solution
Impregnate 2h；
Step 3：The modified polyacrylonitrile precursor that step 2 is obtained puts 80 DEG C of drying 0.5h in an oven, then poly- third
Alkene nitrile precursor is put into pre-oxidation furnace, is heated to 280 DEG C, is pre-oxidized 3h in air；
Step 4：Step 3 is obtained modified polyacrylonitrile oxidization fiber to be put into tube furnace, under the atmosphere of nitrogen with 4 DEG C/
The speed of min is warming up to 1000 DEG C, then keeps the temperature 6h, and sample is taken out after being then cooled to room temperature with the speed of 3 DEG C/min.
Auger electron spectroscopy (AES) and FTIR spectrum (FTIR) analysis are carried out to sample, fiber surface B is measured and contains
It measures as 19.1%, N content 17.8%, and in 1380-1400cm-1There are stronger B-N absorption peak strengths at place.
Comparative example 1
Step 1：Oil removing, decontamination, drying are carried out to polyacrylonitrile surface；
Step 2：Polyacrylonitrile is put into absolute ethyl alcohol and impregnates 2h；
Step 3：The unmodified polypropylene nitrile precursor that step 2 is obtained puts 80 DEG C of drying 0.5h in an oven, then poly-
Acrylonitrile precursor is put into pre-oxidation furnace, is heated to 280 DEG C, is pre-oxidized 3h in air；
Step 4：Step 3 is obtained unmodified polypropylene nitrile oxidization fiber to be put into tube furnace, with 4 under the atmosphere of nitrogen
DEG C/speed of min is warming up to 1000 DEG C, 6h is then kept the temperature, sample is taken out after being then cooled to room temperature with the speed of 3 DEG C/min.
Auger electron spectroscopy (AES) and FTIR spectrum (FTIR) analysis are carried out to sample, fiber surface B is measured and contains
It measures as 0, N content 0.
Boron source in the present invention is boric acid, and boric acid is a kind of lewis acid, has stronger electron-withdrawing power, boron is as non-
Metallic element generates boron nitride structure in carbonization process, has substantially no effect on carbon fiber performance.Nitrogen source is urea, is heated to 160
It DEG C decomposes, generates ammonia, while become cyanic acid, can react in carbonization process with boric acid decomposition product, formation boron nitride structure.
Any one in stirring or ultrasound may be employed in impregnation method mentioned in the present invention.
Also need to emphasize is a little that method of the invention is suitable for the process that various polyacrylonitrile fibrils prepare carbon fiber,
The polyacrylonitrile fibril that such as prepared by copolymerization of acrylonitrile.
Analyze above example as a result, in an oxidizing atmosphere, higher than 400 DEG C, carbon fiber will start to aoxidize, temperature
It may result in carbon fibre composite mechanical properties decrease during higher or even start to aoxidize.If Fig. 1 is unmodified polypropylene nitrile
Cross-section morphology scanning electron microscopic picture after precursor pre-oxidation, it can be seen that unmodified polyacrylonitrile pre-oxidation fiber internal void is dredged
It is loose and uneven, relatively mixed and disorderly；This can cause to introduce substantial amounts of charing defect in carbonization process, and carbon fiber is made to obtain densification degree
Decline, mechanical property is deteriorated.
If Fig. 2 is that boric acid and urea ethanol solution impregnate sample section pattern after modified polyacrylonitrile fibril pre-oxidizes and sweep
Retouch electron microscopic picture, it can be seen that after the pre-oxidation of the polyacrylonitrile fibril of impregnation the densification degree of section preferably and compared with
Uniformly, degree of orientation is preferable, and radial direction otherness makes moderate progress, and obtains the extraordinary PAN-based stabilized fiber of densification degree.
The pre-oxidized fibers of homogeneous are the premises for obtaining high-strength carbon fiber, the pre-oxidized fibers of homogeneous are obtained, by charing
High-strength carbon fiber is made, while the decomposition product of boric acid and urea is uniformly adhered to surface, it can be in table in charing
Layer forms boron nitride coating.
In various embodiments above, boric acid is identical with the additional proportion of urea, but concentration is different, therefore nitridation obtained
The content of boron coating is also different, although the molecular weight of boric acid and urea is not much different, but B atoms can penetrate into fiber
Inside forms certain B-C-N structures, so as to increase the intensity of fiber internal.
Each technical characteristic of embodiment described above can be combined arbitrarily, to make description succinct, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, the scope that this specification is recorded all is considered to be.
The above is the preferred embodiment of the present invention, it is noted that for those skilled in the art
For, without departing from the principles of the present invention, several improvements and modifications can also be made, these improvements and modifications
It should be regarded as protection scope of the present invention.
Claims (7)
- A kind of 1. method for having boron nitride coating carbon fiber using polyacrylonitrile preparation surface, which is characterized in that including following step Suddenly：Step 1：Oil removing, decontamination, drying are carried out to polyacrylonitrile fibril；Step 2：Using absolute ethyl alcohol as solvent, the boric acid urea for being 0.6-0.8mol/L with boric acid and urea configuration boric acid concentration soaks Stain solution；Step 3：The polyacrylonitrile that step 1 is obtained is put into step 2 and obtains impregnating in boric acid urea dipping solution, then dries；Step 4：The polyacrylonitrile that step 3 is obtained, which is put into pre-oxidation furnace, to be pre-oxidized；Step 5：The polyacrylonitrile that step 4 is obtained is put into high temperature process furnances, is heated up under protective gas atmosphere, is kept the temperature, drop Sample is taken out after to room temperature.
- 2. the method according to claim 1 for having boron nitride coating carbon fiber using polyacrylonitrile preparation surface, feature It is, polyacrylonitrile fibril K numbers are any one in 1K, 3K, 6K, 10K in the step 1.
- 3. the method according to claim 1 for having boron nitride coating carbon fiber using polyacrylonitrile preparation surface, feature It is, the molar ratio of boric acid and urea is 2-5 in the step 2:1.
- 4. the method according to claim 1 for having boron nitride coating carbon fiber using polyacrylonitrile preparation surface, feature It is, the time impregnated in the step 3 is 1-4h.
- 5. the method according to claim 4 for having boron nitride coating carbon fiber using polyacrylonitrile preparation surface, feature It is, the Pre oxidation in the step 4 is 260-280 DEG C, and the time of pre-oxidation is 2-3h.
- 6. the method according to claim 1 for having boron nitride coating carbon fiber using polyacrylonitrile preparation surface, feature It is, the protective gas in the step 5 is nitrogen or argon gas.
- 7. the method according to claim 6 for having boron nitride coating carbon fiber using polyacrylonitrile preparation surface, feature It is, the rate of heating and cooling in the step 5 is 2-4 DEG C/min, and holding temperature is 800-1000 DEG C, and soaking time is 4-6h。
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| CN113981569A (en) * | 2021-10-27 | 2022-01-28 | 因达孚先进材料(苏州)有限公司 | Method for producing graphite fiber by catalytic graphitization |
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| CN110241611A (en) * | 2019-06-18 | 2019-09-17 | 南通大学 | A kind of high-temperature resistance carbon fiber magnetism Wave suction composite material and preparation method thereof |
| CN110241611B (en) * | 2019-06-18 | 2021-09-24 | 南通大学 | High-temperature-resistant carbon fiber magnetic wave-absorbing composite material and preparation method thereof |
| CN113981569A (en) * | 2021-10-27 | 2022-01-28 | 因达孚先进材料(苏州)有限公司 | Method for producing graphite fiber by catalytic graphitization |
| CN113981569B (en) * | 2021-10-27 | 2023-06-23 | 因达孚先进材料(苏州)有限公司 | Method for producing graphite fibers by catalytic graphitization |
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