CN1053478C - Method for treating carbon fibre surface - Google Patents
Method for treating carbon fibre surface Download PDFInfo
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- CN1053478C CN1053478C CN96102154A CN96102154A CN1053478C CN 1053478 C CN1053478 C CN 1053478C CN 96102154 A CN96102154 A CN 96102154A CN 96102154 A CN96102154 A CN 96102154A CN 1053478 C CN1053478 C CN 1053478C
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- coating
- oxidation
- charcoal fiber
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- air
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Abstract
The present invention relates to a method of surface treatment of carbon fibers. In the method, the surfaces of the carbon fibers are immersed with a layer of coating solution prepared from organic substances of coating and organic solvents; then, solvent drying is carried out, and coating fibers with solvent volatilizing are oxidized in a gas phase for 10 to 600 seconds at a temperature of 100 to 1000 DEG C. The method combines liquid-phase coating with gas-phase oxidation to modify the surfaces of the carbon fibers, and thus, the method has the advantages that the technological process is greatly simplified, and operation is convenient without pollution. The self strength of the modified carbon fibers and the interlaminar shear strength (ILSS) of composite materials are greatly improved.
Description
The invention belongs to the surface treatment method of charcoal fiber.
The charcoal fiber has been along with space flight and aviation and the reach of science of raw material of wood-charcoal material and the novel enhanced material that emerges since the fifties.Because it has high strength, high-modulus, low-gravity, anti-ablation, excellent properties such as high temperature resistant, corrosion-resistant, has been widely used in various fields.The charcoal fiber is normally as the reinforcing material of matrixes such as resin, metal, charcoal, cement, and the mechanical property of carbon fiber composite depends primarily on the binding ability of mechanical property, fiber and matrix of surface property, fiber self of mechanical property, the fiber of composite elements and the transfer mode of interfacial stress.The lyophobicity of carbon fiber surface makes it can not be fine compound with matrix, and the interlaminar shear strength after compound has only 50-70MPa, has therefore limited its application.Mostly there is own supporting carbon fiber surface processing method in external advanced charcoal fiber manufacturing firm.Present industrialized carbon fiber surface processing method mainly contains ozonization method and anode electrolysis oxidizing process.The disclosed anodizing of people such as J.B.Donnet (Carbon, Vol 27, NO.5 P323 1989) need be washed after oxidation and be dry, and complex procedures is easily introduced impurity.Chinese Academy of Sciences's Shanxi coalification patent " carbon fiber surface treatment method and equipment, (patent No. 8610883.5) " then disclose a kind of employing ozone the charcoal fiber carried out the surface-treated method, this method needs a cover ozone generator, ozone is harmful.Though above-mentioned anodizing and ozone oxidation method can effectively be improved the surface nature of charcoal fiber, improve the interlaminar shear strength of charcoal fibre reinforced composites, but all can damage to some extent, charcoal fiber itself tensile strength is descended or can not improve at least, and environment is had pollution the charcoal fiber itself.
The object of the present invention is to provide a kind of shear strength and charcoal fiber itself tensile strength that can increase substantially the charcoal fibre reinforced composites, equipment is simple, easy to operate, to the free of contamination substantially carbon fiber surface processing method of environment.
Carbon fiber surface processing method of the present invention is that carbon fiber surface is soaked into the coating solution of one deck by coating organic substance and organic solvent preparation, carry out solvent seasoning then, with the coated fiber behind the solvent flashing 100-1000 ℃ of following gaseous oxidation 10 seconds-10 minutes.
The described coated substance of this method can be itself or by coated substance and the formulated solution of organic solvent, the compound concentration of coating solution is for containing coated substance 0-10%.The coating organic substance can be selected from following compounds: phenolic resins, polyvinyl alcohol resin, coal tar pitch, mesophase pitch, asphalt, aliphatic hydrocarbon, aromatic hydrocarbons polycyclic compound and their mixture.
Described organic solvent can be normal heptane, thiacyclohexane, benzene, tetrahydrochysene fall mutter, fat and aromatic compound and their derivative thereof such as methylbenzene, pyridine, quinoline.
The charcoal fiber can form a coating on its surface through soaking into later in the coating solution for preparing, this coating is in the solvent seasoning process, solvent can vapor away, and the temperature of solvent seasoning changes according to the difference of coating solution solvent for use, can learn fully from prior art.
Need to carry out gaseous oxidation through the coating charcoal fiber after the solvent seasoning under 100-1000 ℃ and handled 10 seconds-10 minutes, oxide isolation can be O
2, O
3, NO
2, NO, SO
2, SO
3, CO, CO
2, NH
3, air, steam and their mist.
Oxide isolation is from the convenient and low-cost angle consideration of source of the gas, preferably air or CO
2
Gaseous oxidation can be finished and also can divide second oxidation to finish in a step.
This method is handled in the charcoal fiber process, behind the coating organic substance soakage layer, can fill up the hole defect of carbon fiber surface, and these defectives cause the reason that the charcoal fibre strength descends just.Through after the gaseous oxidation, the coating organic matter not only can condensation and also with the unsaturated carbon atom generation chemical reaction of charcoal fiber fault location, form chemical bond, thereby improved the intensity of charcoal fiber effectively, also improved simultaneously the surface nature of charcoal fiber, the interlaminar shear strength of charcoal fiber reinforcement degree composite is significantly improved.
The present invention adopts method that liquid phase coating and gaseous oxidation combine that modification is carried out on the surface of charcoal fiber and handles, make technical process greatly simplify, easy to operate, pollution-free.Charcoal fiber self intensity after modification is handled and the interlaminar shear strength (ILSS) of composite all have raising by a relatively large margin.This method can be directly and the online supporting use of charcoal fiberline.
Embodiment 1
Getting tensile strength is the polyacrylonitrile charcoal fiber A of 2279MPa, is mixed with the coating solution that contains mesophase pitch 0.4-1% with mesophase pitch and oxolane.Above-mentioned charcoal fiber is done to carry out drying after the infiltration in coating solution slightly.Under 800-1000 ℃, contain 1.0%CO then
2Nitrogen in handled 2 minutes, again through 400 ℃ of air oxidations in short-term, make modification and handle the charcoal fiber.
Embodiment 2
Getting tensile strength is the polyacrylonitrile charcoal fiber B of 2568MPa, is mixed with the coating solution of 0.1-0.5% by asphalt and normal heptane.After soaking into the canal layer, oxidation processes is 3 minutes in 200-300 ℃ of air, and then handles in short-term through 500 ℃ of air, will make modification and handle the charcoal fiber.
Embodiment 3
Getting tensile strength is the polyacrylonitrile charcoal fiber C of 3063MPa, contains the coating solution of naphthane 0.5-2.0% with naphthane and benzene preparation.Contain SO at 800-1000 ℃ after the solution drying
2Handled in 1.2% the air gas mixture 1 minute, again through 500 ℃ of air oxidation processes in short-term, the charcoal fiber is handled in modification.
Embodiment 4
Getting tensile strength is the polyacrylonitrile charcoal fiber D of 2669MPa, contains the coating solution of lutidines 1-5% with lutidines and thiacyclohexane preparation.In 800-1000 ℃ of nitrogen mixture body that contains 0.5% water vapour and 0.5% air, handled 3 minutes after the solvent seasoning, handle in short-term through 450 ℃ of air again, the charcoal fiber is handled in modification.
Embodiment 5
Getting tensile strength is the polyacrylonitrile charcoal fiber E of 2568MPa, contains the coating solution of phenolic resins 0.01-0.1% with phenolic resins and normal heptane preparation.Oxidation 2 minutes in 500-600 ℃ air after the solution drying, the charcoal fiber is handled in modification.
Embodiment 6
Getting tensile strength is the polyacrylonitrile charcoal fiber F of 2507MPa, contains the coating solution of 9,10 1 dimethylnaphthalene 0.2-1.0% with 9,10 1 dimethylnaphthalenes and methylbenzene preparation.The solution drying after 400-550 ℃ air oxidation 1-3 minute, the charcoal fiber is handled in modification.
Embodiment 7
Getting tensile strength is the polyacrylonitrile charcoal fiber G of 2853MPa, contains the coating solution of coal tar asphalt 0.2-0.8% with coal tar asphalt and quinoline preparation.Oxidation 1.5 minutes in 800-1000 ℃ of nitrogen that contains 1% CO after the solution drying, again through 500-600 ℃ of air oxidation processes in short-term, charcoal fiber G is handled in modification.
Embodiment 8
Getting tensile strength is the polyacrylonitrile charcoal fiber H of 3026MPa, soaks into deep layer with cyclohexane, through 150-250 ℃ of air oxidation 5 minutes, oxidation processes in short-term in 500-600 ℃ of air then, the charcoal fiber is handled in modification.
The test data of the interlaminar shear strength (ILSS) of self tensile strength coefficient of variation of the charcoal fiber after handling through modification in the foregoing description and charcoal fiber-reinforced resin (use the AG-80 resin) composite (CFRP) is listed in the table below and does a comparison with the data before the unmodified processing.
| The charcoal fiber | Tensile strength MPa | Variation number system (%) | Interlaminar shear strength (MPa) | |||
| Before the modification | After the modification | Before the modification | After the modification | Before the modification | After the modification | |
| A | 2279 | 3040 | 15.51 | 6.60 | 68.0 | 90.1 |
| B | 2568 | 3614 | 15.51 | 5.11 | 71.1 | 103.1 |
| C | 3063 | 3578 | 18.17 | 10.35 | 70.2 | 93.8 |
| D | 2669 | 3346 | 10.96 | 7.36 | 69.0 | 90.5 |
| E | 2568 | 3365 | 15.15 | 6.60 | 70.0 | 91.0 |
| F | 2507 | 3200 | 14.46 | 7.32 | 70.1 | 91.2 |
| G | 2853 | 3407 | 11.23 | 4.40 | 68.7 | 91.4 |
| H | 3026 | 3548 | 12.48 | 11.97 | 69.1 | 86.4 |
Listed charcoal fiber self tensile strength and the data of interlaminar shear strength obtain according to GB GB3357-82, GB3362-82 analytical test in the last table.
Claims (7)
1. the method for a carbon fiber surface modification, it is characterized in that carbon fiber surface is soaked into the coating solution of one deck by coating organic substance and organic solvent preparation, carry out solvent seasoning then, will vapor away the gaseous oxidation 10 seconds-5 minutes under 100-1000 ℃ temperature of coating charcoal fiber behind the solvent.
2. the method for claim 1 is characterized in that the compound concentration of described coating solution is 0.01-10% for containing coating organic substance percentage by weight.
3. method as claimed in claim 1 or 2 is characterized in that described coating organic substance can be phenolic resins, polyvinyl alcohol resin, coal tar pitch, mesophase pitch, asphalt, aliphatic hydrocarbon, aromatic hydrocarbons polycyclic compound and their mixture.
4. method as claimed in claim 1 or 2 is characterized in that described organic solvent can be fat and aromatic compound and their derivatives thereof such as normal heptane, cyclohexane, benzene, oxolane, pyridine, quinoline.
5. the method for claim 1 is characterized in that described gaseous oxidation medium can be O
2, O
3, NO
2, NO, SO
2, CO, CO
2, NH
3, air, steam and their mist.
6. the method for claim 1, the oxide isolation that it is characterized in that described gaseous oxidation is air or CO preferably
2
7. described method as claimed in claim 1, but it is characterized in that described gaseous oxidation oxidation step finishes, also can divide second oxidation to finish.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96102154A CN1053478C (en) | 1996-02-14 | 1996-02-14 | Method for treating carbon fibre surface |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96102154A CN1053478C (en) | 1996-02-14 | 1996-02-14 | Method for treating carbon fibre surface |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1157354A CN1157354A (en) | 1997-08-20 |
| CN1053478C true CN1053478C (en) | 2000-06-14 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96102154A Expired - Fee Related CN1053478C (en) | 1996-02-14 | 1996-02-14 | Method for treating carbon fibre surface |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1320181C (en) * | 2005-08-24 | 2007-06-06 | 哈尔滨工业大学 | Modification method of interface between carbon fiber and non-polar resin |
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| CN101413210B (en) * | 2008-11-12 | 2011-08-31 | 东华大学 | Method for carbon fiber surface modification of plasma coated with silicon dioxide by plasma treatment |
| CN101532240B (en) * | 2008-12-19 | 2012-05-09 | 东华大学 | Method for modifying nanometer sol Vectran fiber by plasma treatment |
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| CN102912637B (en) * | 2012-11-16 | 2015-02-11 | 中复神鹰碳纤维有限责任公司 | Carbon fiber sizing agent |
| CN103031724B (en) * | 2013-01-17 | 2014-08-27 | 哈尔滨工业大学 | Preparation method for carbon fiber surface composite coating |
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| CN103061111A (en) * | 2013-01-17 | 2013-04-24 | 哈尔滨工业大学 | Preparation method of modified coating of carbon fiber surface |
| CN103015163A (en) * | 2013-01-17 | 2013-04-03 | 哈尔滨工业大学 | Preparation method of carbon fiber surface composite coating |
| CN106192115A (en) * | 2016-09-19 | 2016-12-07 | 西安航天复合材料研究所 | A kind of preparation method of carbon fiber stitching thread |
| CN110424161B (en) * | 2019-08-11 | 2021-12-14 | 西南石油大学 | HfZrB on carbon fiber surface2Preparation method of-SiBNC composite coating |
| CN111394834B (en) * | 2020-05-15 | 2022-06-17 | 北京先进碳能科技有限公司 | Preparation method of mesophase pitch carbon fiber with rough surface |
| CN113622185A (en) * | 2021-08-30 | 2021-11-09 | 陕西天策新材料科技有限公司 | Method for improving surface activity of asphalt-based graphite carbon fiber |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1082131A (en) * | 1992-08-11 | 1994-02-16 | 中国科学院山西煤炭化学研究所 | SURFACE TREATMENT OF CARBON FIBER method and device |
-
1996
- 1996-02-14 CN CN96102154A patent/CN1053478C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1082131A (en) * | 1992-08-11 | 1994-02-16 | 中国科学院山西煤炭化学研究所 | SURFACE TREATMENT OF CARBON FIBER method and device |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1320181C (en) * | 2005-08-24 | 2007-06-06 | 哈尔滨工业大学 | Modification method of interface between carbon fiber and non-polar resin |
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|---|---|
| CN1157354A (en) | 1997-08-20 |
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