CN102021678A - Method for surface treatment of carbon fiber - Google Patents
Method for surface treatment of carbon fiber Download PDFInfo
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- CN102021678A CN102021678A CN 201010284026 CN201010284026A CN102021678A CN 102021678 A CN102021678 A CN 102021678A CN 201010284026 CN201010284026 CN 201010284026 CN 201010284026 A CN201010284026 A CN 201010284026A CN 102021678 A CN102021678 A CN 102021678A
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Abstract
The invention relates to a method for the surface treatment of carbon fibers, which comprises the following steps: 1) preparing ozone water, wherein the concentration of the ozone water is 5-150 mg/L and the temperature is 5-45 DEG C; 2) soaking the carbon fiber, that is, soaking the carbon fiber processed by high temperature carbonization in the ozone water for 0.5-10 min to obtain a carbon fiber with composite properties. The invention solves the technical problems that existing methods for the surface treatment of carbon fibers allow the easy introduction of electrolyte impurities and thus the carbon fibers are polluted; the present invention improves surface properties of carbon fibers and increases the interlaminar shear strength of carbon fiber reinforced composite materials.
Description
Technical field
The present invention relates to the new material production field, relate to the aftertreatment technology in the carbon fiber preparation process, be specifically related to a kind of method of surface treatment of carbon fibers.
Background technology
Carbon fiber is a kind of novel metalloid material, has high specific strength, high ratio modulus, high temperature resistant, corrosion-resistant, creep resistant, low-thermal-expansion, high conduction and a series of excellent properties such as heat conduction, self-lubricating; And as fiber also have flexibility and can compile, weaving property, be widely used in civilian industries such as leading-edge fields such as space flight and aviation, national defense and military and senior sports goods, medicine equipment, become one of main enhancing body of advanced composite material, be described as the most vital new material in 21 century.
Carbon fiber is to utilize its phosphorus content that organic fiber makes through technical process such as pre-oxidation, low-temperature carbonization and high temperature cabonization in the new carbon more than 90%.Because carbonization treatment in high temperature inert atmosphere along with the volatilization of non-carbon and the enrichment of carbon, reduces its surface-activity, surface tension reduces, with the wettability variation of matrix resin, cause the interlaminar shear strength of its composite to reduce, can not reach the use designing requirement.In order to make carbon fiber surface change lyophily into by lyophobicity, need carry out surface treatment to it, improve its interlaminar shear strength, satisfy design and practical requirement.Carbon fiber surface treatment method is more, but online matching used method is less, and at present widely used is the anode electrolysis oxidizing process.As everyone knows, through the residual a certain amount of electrolyte of carbon fiber surface after the anodized, need to wash, otherwise will influence carbon fiber and performance of composites thereof through washing step.Therefore, cause the aftertreatment technology and the equipment complexity of carbon fiber production process, and in the anode electrolysis oxidation processes, easily introduce electrolyte impurity, pollute carbon fiber.
Summary of the invention
In order to solve the technical problem that existing carbon fiber surface treatment method is introduced electrolyte impurity easily, polluted carbon fiber, the purpose of this invention is to provide a kind of method of surface treatment of carbon fibers.
Technical solution of the present invention:
A kind of method of surface treatment of carbon fibers, its special character is: may further comprise the steps:
1] preparation Ozone Water: the concentration of described Ozone Water is 5～150mg/L, and temperature is 5～45 ℃;
2] soak carbon fiber: the carbon fiber after high temperature cabonization is handled soaks 0.5～10min in above-mentioned Ozone Water, obtain having the carbon fiber of composite performance.
Above-mentioned steps comprises that also thereby the oxygen concentration of carbon of measuring the carbon fiber finished surface is than the step of adjusting consistency of ozone water and soak time: when the oxygen concentration of carbon than less than 0.02 the time, need to increase consistency of ozone water and soak time, when the oxygen concentration of carbon than greater than 0.30 the time, need to reduce consistency of ozone water and soak time.
Above-mentioned oxygen concentration of carbon is 0.08～0.20 than scope.
Above-mentioned steps 1] in Ozone Water be that to adopt pure air or oxygen be that source of the gas produces ozone through ozone generator, mixed with deionized water again through static mixer.
The concentration of above-mentioned Ozone Water is 50～100mg/L, and temperature is 15～25 ℃.
Above-mentioned steps 2] time of soaking carbon fiber is 1～5min.
The advantage that the present invention had:
1, the inventive method adopts certain density Ozone Water that carbon fiber surface is carried out the oxide impregnation processing, has improved the surface characteristic of carbon fiber, thereby has improved the interlaminar shear strength of carbon fibre reinforced composite.
2, the inventive method have that equipment is simple, treatment effeciency is high, treatment effect is good, to the free of contamination substantially advantage of environment, handle the back carbon fiber through this method simultaneously, do not need to carry out the washing process washing, make the aftertreatment technology of carbon fiber production process simplify, minimizing improves the mechanical property of carbon fiber to the mechanical damage of carbon fiber.
3, method of the present invention can be directly and the online supporting use of existing carbon fiber production line, and have that process equipment is simple, treatment effeciency is high, treatment effect is good, and to the free of contamination substantially advantage of environment.
The specific embodiment
The method of surface treatment of carbon fibers of the present invention may further comprise the steps:
1, preparation Ozone Water: the concentration of Ozone Water is 5～150mg/L, is preferably 50～100mg/L; Temperature is 5～45 ℃; Be preferably 15～25 ℃;
2, soak carbon fiber: the carbon fiber after high temperature cabonization is handled soaks 0.5～10min in above-mentioned Ozone Water, obtain having the carbon fiber of composite performance.
For the cleanliness factor that guarantees Ozone Water and steady concentration, controllability, the concentration of Ozone Water is 5～150mg/L, is preferably 50～100mg/L; Ozone Water generally adopts pure air or oxygen is that source of the gas produces ozone through ozone generator, and mixed through static mixer with deionized water again, its concentration satisfies above-mentioned scope.If consistency of ozone water is lower than 5mg/L, then the surface treatment of carbon fibers time longer, treatment effeciency is low, is unfavorable for the online supporting use of industrialization; If consistency of ozone water is higher than 150mg/L, then the surface treatment of carbon fibers etching is serious and uniformity is relatively poor, and consistency of ozone water is too high simultaneously, increases production cost.The time of described surface treatment of carbon fibers is relevant with the concentration of Ozone Water, is generally 0.5～10min, is preferably 1-5min; If the surface treatment of carbon fibers time, then the carbon fiber surface etching was insufficient less than 0.5min, cause the composite performance of carbon fiber and matrix resin relatively poor; If the surface treatment of carbon fibers time, then the carbon fiber surface overetch caused tensile strength of carbon fibers to reduce, and is unfavorable for the online supporting use of industrialization simultaneously, also can increase the carbon fiber production cost greater than 10min; The described surface treatment of carbon fibers time is meant the time of staying of carbon fiber in Ozone Water.The Ozone Water temperature of described surface treatment of carbon fibers has certain requirement, is generally 5～45 ℃, is preferably 15～25 ℃; If the temperature of Ozone Water is too high, the ozone that then is dissolved in the water will be decomposed into oxygen, and surface-treated efficient is lower.
In order to guarantee to have good composite performance between carbon fiber and the matrix resin, the oxygen concentration of carbon of the carbon fiber surface after the process surface treatment is 0.02～0.30 than (O/C), is preferably 0.08～0.20.If the oxygen concentration of carbon ratio of carbon fiber surface is lower than 0.02, the oxygen-containing functional group in the carbon fiber is very few, with the adhesive property reduction of resin matrix, and then the reduction of the interlaminar shear strength of carbon fibre composite, need to increase consistency of ozone water and soak time this moment; If the oxygen concentration of carbon ratio of carbon fiber surface is higher than 0.30, oxygen-containing functional group in the carbon fiber is too much, reduced adhesive property on the contrary with resin matrix, the tensile strength of carbon fiber itself reduces significantly owing to its surperficial overetch simultaneously, cause the mechanical property of carbon fibre composite to reduce, need to reduce consistency of ozone water and soak time this moment.
Carbon fiber surface treatment method provided by the present invention is handled with traditional anode electrolysis oxidized surface and is compared, and the main distinction is to adopt certain density Ozone Water that carbon fiber surface is carried out impregnation process.The decomposition mechanism of ozone in pure water is extremely complicated, the hydroxide ion (OH in it and the water
-) generation series reaction generation hydroxyl radical free radical (OH), hydroxyl radical free radical has extremely strong oxidisability (standard oxidationreduction potential is 2.85V), be only second to fluorine (standard oxidationreduction potential 3.06V), the strong oxidizer that belongs to the ball electron type, and the selectivity height of oxidation reaction are easily with two key reactions, therefore can carry out oxidation to carbon fiber surface, its result not only introduces oxygen-containing functional group on its surface, and can eliminate its blemish, and carbon fiber strength is increased.Described surface-treated treatment media is Ozone Water and non-electrolytic solution, therefore need not to carry out washing process after the surface treatment of carbon fibers washs, the result makes the aftertreatment technology of carbon fiber production process simplify, reduce the mechanical damage of washing step, can improve the mechanical property of carbon fiber to a certain extent carbon fiber.
With the 3K polyacrylonitrile-based precursor is raw material, carries out pre-oxidation treatment in 180～275 ℃ air atmosphere, wherein, 10 gradient warm areas from low to high is set in the said temperature scope, and the preparation volume density is 1.35g/cm
3Pre-oxidized fibers.
Above-mentioned preparation pre-oxidized fibers is carried out low-temperature carbonization handle in 300～900 ℃ nitrogen atmosphere, in 1200-1600 ℃ nitrogen atmosphere, carry out high temperature cabonization then and handle, make not surface-treated carbon fiber.
With above-mentioned not surface-treated 3K carbon fiber is raw material, adopts above-mentioned technological process to carry out post processing, and wherein surface treatment condition table 1 is listed, and making tensile strength is that 3.95GPa, Young's modulus are the carbon fiber of 228GPa.
In order to estimate the effect of surface treatment of carbon fibers, adopt the method for the interlaminar shear strength (ILSS) of test carbon fibre composite to estimate among the present invention, specifically carry out according to the method for testing of GB GB3357-82.
ILSS test result such as the table 1 of each embodiment is listed among the present invention.
The surface treatment condition of the different embodiment of table 1 and the ILSS result of carbon fibre composite thereof
Claims (6)
1. the method for a surface treatment of carbon fibers is characterized in that: may further comprise the steps:
1] preparation Ozone Water: the concentration of described Ozone Water is 5～150mg/L, and temperature is 5～45 ℃;
2] soak carbon fiber: the carbon fiber after high temperature cabonization is handled soaks 0.5～10min in above-mentioned Ozone Water, obtain having the carbon fiber of composite performance.
2. the method for surface treatment of carbon fibers according to claim 1, it is characterized in that: thus described step comprises that also the oxygen concentration of carbon of measuring the carbon fiber finished surface is than the step of adjusting consistency of ozone water and soak time: when the oxygen concentration of carbon than less than 0.02 the time, need to increase consistency of ozone water and soak time, when the oxygen concentration of carbon than greater than 0.30 the time, need to reduce consistency of ozone water and soak time.
3. the method for surface treatment of carbon fibers according to claim 2, it is characterized in that: described oxygen concentration of carbon is 0.08～0.20 than scope.
4. according to the method for claim 1 or 2 or 3 described surface treatment of carbon fibers, it is characterized in that: described step 1] in Ozone Water be that to adopt pure air or oxygen be that source of the gas produces ozone through ozone generator, mixed with deionized water again through static mixer.
5. the method for surface treatment of carbon fibers according to claim 4, it is characterized in that: the concentration of described Ozone Water is 50～100mg/L, temperature is 15～25 ℃.
6. the method for surface treatment of carbon fibers according to claim 5 is characterized in that: described step 2] time of soaking carbon fiber is 1～5min.
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| CN 201010284026 CN102021678A (en) | 2010-09-16 | 2010-09-16 | Method for surface treatment of carbon fiber |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104514085A (en) * | 2013-09-29 | 2015-04-15 | 泰安鲁普耐特塑料有限公司 | Production method for basalt fiber protective net |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3723607A (en) * | 1970-07-16 | 1973-03-27 | Celanese Corp | Surface modification of carbon fibers |
| KR20040070397A (en) * | 2003-02-03 | 2004-08-09 | 한국화학연구원 | A method for preparing a carbon fiber reinforced composite having an improved mechanical property |
| CN101189373A (en) * | 2004-10-22 | 2008-05-28 | 海珀里昂催化国际有限公司 | Improved ozonolysis of carbon nanotubes |
| CN101290836A (en) * | 2008-06-13 | 2008-10-22 | 陕西师范大学 | Method for enhancing specific capacitance of phenolic resin based activated carbon fiber |
| JP2009079344A (en) * | 2007-09-06 | 2009-04-16 | Mitsubishi Rayon Co Ltd | Surface treatment method of carbon fiber |
-
2010
- 2010-09-16 CN CN 201010284026 patent/CN102021678A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3723607A (en) * | 1970-07-16 | 1973-03-27 | Celanese Corp | Surface modification of carbon fibers |
| KR20040070397A (en) * | 2003-02-03 | 2004-08-09 | 한국화학연구원 | A method for preparing a carbon fiber reinforced composite having an improved mechanical property |
| CN101189373A (en) * | 2004-10-22 | 2008-05-28 | 海珀里昂催化国际有限公司 | Improved ozonolysis of carbon nanotubes |
| JP2009079344A (en) * | 2007-09-06 | 2009-04-16 | Mitsubishi Rayon Co Ltd | Surface treatment method of carbon fiber |
| CN101290836A (en) * | 2008-06-13 | 2008-10-22 | 陕西师范大学 | Method for enhancing specific capacitance of phenolic resin based activated carbon fiber |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104514085A (en) * | 2013-09-29 | 2015-04-15 | 泰安鲁普耐特塑料有限公司 | Production method for basalt fiber protective net |
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Application publication date: 20110420 |