CN105696313A - Surface modification method of carbon fibers - Google Patents
Surface modification method of carbon fibers Download PDFInfo
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- CN105696313A CN105696313A CN201610059169.3A CN201610059169A CN105696313A CN 105696313 A CN105696313 A CN 105696313A CN 201610059169 A CN201610059169 A CN 201610059169A CN 105696313 A CN105696313 A CN 105696313A
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- carbon fiber
- electrophoretic deposition
- graphene oxide
- surface modification
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—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
- D06M11/73—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 carbon or compounds thereof
- D06M11/74—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 carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/40—Fibres of carbon
Abstract
The invention relates to a surface modification method of carbon fibers. Graphene oxide is used as a surface modifying material of the carbon fibers; and the graphene oxide is deposited on the carbon fibers through ultrasonic-assisted electrophoresis and can form a composite material with high performance. The surface modification method is low in cost, simple to operate and strong in applicability. The surface modification method of the carbon fibers has the advantages that equipment for surface modification of the carbon fiber is low in investment cost, and the method is low in cost, simple in operation, strong in applicability, good in treatment effect, small in fiber performance loss and reliable in quality. The modification time is greatly shortened, the use amount of chemicals and the cost of the product are reduced, and the environmental pollution is reduced, so that the surface modification method is suitable for industrial production.
Description
Technical field
The present invention relates to and belongs to carbon fiber surface modification technical field, and the method for the surface modification of a kind of carbon fiber, the method particularly relating to the surface modification of a kind of carbon fiber ultrasonic wave added electrophoretic deposition graphene oxide。
Background technology
Carbon fiber refers to that the phosphorus content fibrous material more than more than 85%, including carbon fibre and graphite fibre through high temperature cabonization。Carbon fibre is organic fiber after 1000～2300 DEG C process, and phosphorus content is the fiber of 85%～95%；Graphite fibre is that organic fiber is through more than 2300 DEG C process, phosphorus content fiber more than 98%, carbon fiber is as a kind of high-performance fiber, become the most important reinforcing material of polymer matrix composites in recent years because having the characteristics such as specific strength height, specific modulus is high, thermal coefficient of expansion is little, coefficient of friction is low, resistance to low temperature is good, be widely used in Aero-Space component and sports goods。Carbon fiber surface is inert, and specific surface area is little, and edge active carbon atom is few, surface can low and resin wellability and two-phase interface bad adhesion, composite interlayer shear strength (InterlaminarShearingStrength, ILSS) is low。Thus affecting the performance of composite material combination property, constrain the carbon fiber further genralrlization application in advanced field of compound material。In order to improve the performance of carbon fiber enhancement resin base composite material, carbon fiber surface must be modified, to improve the cementitiousness of carbon fiber and other materials。
For improving the adhesion of carbon fiber and resin matrix etc., improving the shearing strength between layers of composite and the surface treatment that must carry out。Purpose is to increase the polar group such as functional group such as carboxyl, carbonyl and lactone of carbon fiber, increases surface area, improves the wellability with resin matrix and cohesive force。The current method that carbon fiber surface is modified is more, mainly includes (1) liquid phase oxidation (2) plasma processing method (3) anode electrolysis or electrodeposition process method (4) ozonization method (5) vapour phase oxidation process (6) surface high-energy radiation method (7) modification by copolymerization method and coupling agent treatment etc.。These methods can substantially meet the modified needs of Properties of Carbon Fiber Surface, but it is complex to there is technique, processes the time long, the problems such as surface modification is uneven。
Carbon fiber is as excellent composite reinforcing material, in its actual application, in order to repair defect, improves performance further, and meets different user demands, often at the material that carbon fiber surface deposition is new。
This material of graphene oxide has intensity best in known materials, excellent electric conductivity and heat conductivity, and current existing electrophoretic deposition Treatment of Carbon process for modifying surface patent is without reference to the method for the surface modification of ultrasonic wave added electrophoretic deposition graphene oxide。
Summary of the invention
Solve the technical problem that
In order to avoid the deficiencies in the prior art part, the present invention proposes the method for the surface modification of a kind of carbon fiber。
Technical scheme
The method of the surface modification of a kind of carbon fiber, it is characterised in that step is as follows:
Step 1: carbon fiber is carried out surface destarch process；
Step 2: add graphene oxide in deionized water, supersound process 10-50min, obtain the graphene oxide water solution that graphene oxide concentration is 0.02-1g/L；
Step 3: using graphene oxide water solution as electrophoretic deposition liquid, carbon fiber connects positive source and is placed in electrophoretic deposition pond and carries out electrophoretic deposition；DC power output voltage during electrophoretic deposition is 5-25V electrophoretic deposition, introduces 40-80W, 30-50kHz ultrasonic assistant, by the carbon fiber dried after ultrasonic wave added electrophoretic deposition in electrophoretic deposition process。
Described step 1 destarch processes: put into by carbon fiber in acetone soln, reacts 24h under 70 DEG C of constant temperatures, uses dehydrated alcohol and deionized water alternately to clean for several times, then by the 80 DEG C of dry 24h of carbon fiber after washing。
The positive source pole piece of described step 3 electrophoretic deposition is carbon or copper electrode。
The power cathode pole piece of described step 3 electrophoretic deposition is graphite electrode。
Described step 3 electrophoretic deposition DC power output voltage is 5V, 10V, 15V or 20V。
Described carbon fiber is any one in unidirectional long fibre cloth, two-way textile sheet, random chopped fiber or its multiple combination。
The preparation of the graphene oxide that described step 2 adopts is: 1, in ice-water bath, graphite powder and sodium nitrate are mixed with concentrated sulphuric acid, adds potassium permanganate, keeps less than 2 DEG C sustained response 1h, obtain mixture A；Wherein the ratio of concentrated sulphuric acid volume and sodium nitrate quality is the mass ratio that mass ratio is 2:1, potassium permanganate and sodium nitrate of 40ml:1g, graphite powder and sodium nitrate is 6:1；2, mixture A being transferred to 35 DEG C of water-bath 30min, add deionized water to 3 times that volume is mixture A, temperature obtains mixture B after rising to 98 DEG C of continuation reaction 15min；3, by mixture B dilute, and process with the hydrogenperoxide steam generator of mass fraction 30%, by solution sucking filtration and with deionized water wash to filtrate in neutrality, within 6 hours, obtain graphite oxide by dry under 40～60 DEG C of vacuum conditions for precipitate；4) graphite oxide and water are made into suspension, imposing supersound process 60～100min, obtain graphene oxide solution, after graphene oxide solution is dried 5h under 40～60 DEG C of vacuum conditions, it is thus achieved that graphene oxide。
Beneficial effect
The method of the surface modification of a kind of carbon fiber that the present invention proposes, adopts graphene oxide as the surface modifying material of carbon fiber, graphene oxide passes through ultrasonic wave added electrophoretic deposition on carbon fiber, high performance composite can be formed, cost of the present invention is low, simple to operate, and the suitability is strong。The graphene oxide deposition carbon fiber of the present invention is graphene oxide deposition to be obtained to the carbon fiber processed by ultrasonic wave added electrophoretic deposition method。
It is an advantage of the current invention that carbon fiber surface modification device therefor investment cost is low, invention cost is low, simple to operate, the suitability strong, the loss of high treating effect, fibre property is little, reliable in quality。Shorten modification time in a large number, reduce chemicals usage and product cost, reduce environmental pollution, it is adaptable to industrialized production。
Detailed description of the invention
In conjunction with embodiment, the invention will be further described:
Example 1:(1) carbon fiber is put in acetone soln, under 70 DEG C of constant temperatures, react 24h, use dehydrated alcohol and deionized water alternately to clean for several times, then constant weight will be dried at 80 DEG C of carbon fiber after washing。(2) add graphene oxide in deionized water, supersound process 30min, obtain the graphene oxide water solution that graphene oxide concentration is 0.2g/L。(3) graphene oxide water solution step 2 obtained adds in electrophoretic deposition pond as electrophoretic deposition liquid, copper electrode is as anode pole piece, carbon fiber pretreated for step 1 is connected positive source, it is 20V electrophoretic deposition that graphite electrode connection power cathode carries out DC power output voltage, electrophoretic deposition process introduces 60W, 40kHz ultrasonic assistant, constant weight will be dried at 80 DEG C of the carbon fiber after ultrasonic wave added electrophoretic deposition。
Example 2:(1) carbon fiber is put in acetone soln, under 70 DEG C of constant temperatures, react 24h, use dehydrated alcohol and deionized water alternately to clean for several times, then by the carbon fiber dried after washing。(2) add graphene oxide in deionized water, supersound process 35min, obtain the graphene oxide water solution that graphene oxide concentration is 0.25g/L。(3) graphene oxide water solution step 2 obtained adds in electrophoretic deposition pond as electrophoretic deposition liquid, carbon fiber pretreated for step 1 is connected positive source and carries out electrophoretic deposition, DC power output voltage during electrophoretic deposition is 15V, electrophoretic deposition process introduces 50W, 50kHz ultrasonic assistant, by the carbon fiber dried after ultrasonic wave added electrophoretic deposition。
Example 3:(1) carbon fiber is put in acetone soln, under 70 DEG C of constant temperatures, react 24h, use dehydrated alcohol and deionized water alternately to clean for several times, then by the carbon fiber dried after washing。(2) add graphene oxide in deionized water, supersound process 40min, obtain the graphene oxide water solution that graphene oxide concentration is 0.5g/L。(3) graphene oxide water solution step 2 obtained adds in electrophoretic deposition pond as electrophoretic deposition liquid, carbon fiber pretreated for step 1 is connected positive source and carries out electrophoretic deposition, DC power output voltage during electrophoretic deposition is 25V, electrophoretic deposition process introduces 40W, 30kHz ultrasonic assistant, by the carbon fiber dried after ultrasonic wave added electrophoretic deposition。
Claims (7)
1. the method for the surface modification of a carbon fiber, it is characterised in that step is as follows:
Step 1: carbon fiber is carried out surface destarch process；
Step 2: add graphene oxide in deionized water, supersound process 10-50min, obtain the graphene oxide water solution that graphene oxide concentration is 0.02-1g/L；
Step 3: using graphene oxide water solution as electrophoretic deposition liquid, carbon fiber connects positive source and is placed in electrophoretic deposition pond and carries out electrophoretic deposition；DC power output voltage during electrophoretic deposition is 5-25V electrophoretic deposition, introduces 40-80W, 30-50kHz ultrasonic assistant, by the carbon fiber dried after ultrasonic wave added electrophoretic deposition in electrophoretic deposition process。
2. the method for the surface modification of carbon fiber according to claim 1, it is characterized in that: described step 1 destarch processes and is: put into by carbon fiber in acetone soln, 24h is reacted under 70 DEG C of constant temperatures, dehydrated alcohol and deionized water is used alternately to clean for several times, then by the 80 DEG C of dry 24h of carbon fiber after washing。
3. the method for the surface modification of carbon fiber according to claim 1, it is characterised in that: the positive source pole piece of described step 3 electrophoretic deposition is carbon or copper electrode。
4. the method for the surface modification of carbon fiber according to claim 1, it is characterised in that: the power cathode pole piece of described step 3 electrophoretic deposition is graphite electrode。
5. the method for the surface modification of carbon fiber according to claim 1, it is characterised in that: described step 3 electrophoretic deposition DC power output voltage is 5V, 10V, 15V or 20V。
6. the method for the surface modification of carbon fiber according to claim 1, it is characterised in that: described carbon fiber is any one in unidirectional long fibre cloth, two-way textile sheet, random chopped fiber or its multiple combination。
7. the method for the surface modification of carbon fiber according to claim 1, it is characterized in that: the preparation of the graphene oxide that described step 2 adopts is: 1, in ice-water bath, graphite powder and sodium nitrate are mixed with concentrated sulphuric acid, adds potassium permanganate, keep less than 2 DEG C sustained response 1h, obtain mixture A；Wherein the ratio of concentrated sulphuric acid volume and sodium nitrate quality is the mass ratio that mass ratio is 2:1, potassium permanganate and sodium nitrate of 40ml:1g, graphite powder and sodium nitrate is 6:1；2, mixture A being transferred to 35 DEG C of water-bath 30min, add deionized water to 3 times that volume is mixture A, temperature obtains mixture B after rising to 98 DEG C of continuation reaction 15min；3, by mixture B dilute, and process with the hydrogenperoxide steam generator of mass fraction 30%, by solution sucking filtration and with deionized water wash to filtrate in neutrality, within 6 hours, obtain graphite oxide by dry under 40～60 DEG C of vacuum conditions for precipitate；4) graphite oxide and water are made into suspension, imposing supersound process 60～100min, obtain graphene oxide solution, after graphene oxide solution is dried 5h under 40～60 DEG C of vacuum conditions, it is thus achieved that graphene oxide。
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106192363A (en) * | 2016-08-11 | 2016-12-07 | 西北工业大学 | A kind of method of the surface modification of carbon fiber plasma grafting graphene oxide |
| CN106637923A (en) * | 2016-10-17 | 2017-05-10 | 哈尔滨工业大学 | Method of quickly and continuously depositing graphene on surface of electric-conductive fibers |
| CN108286187A (en) * | 2017-12-26 | 2018-07-17 | 山东大学 | A kind of preparation method of silane coupling agent auxiliary electrophoretic deposition initiated oxidation graphene modified carbon fiber |
| CN109733017A (en) * | 2019-01-03 | 2019-05-10 | 南京航空航天大学 | Containing graphene/resin/carbon fiber modifying electrothermal layer composite material, preparation method and use |
| CN109750492A (en) * | 2018-12-20 | 2019-05-14 | 山东大学 | A kind of surface treatment method of carbon cloth surfaces homoepitaxial carbon nanotube early period |
| CN109837740A (en) * | 2017-11-27 | 2019-06-04 | 四川东邦碳纤维材料有限公司 | A kind of surface treatment method of carbon fiber and the carbon fiber of preparation |
| CN110904774A (en) * | 2019-12-02 | 2020-03-24 | 哈尔滨学院 | Modular self-snow-melting pavement based on graphene |
| CN111675286A (en) * | 2020-06-01 | 2020-09-18 | 重庆三峡学院 | Modified carbon fiber cathode material, preparation method and application |
| CN113308882A (en) * | 2021-07-18 | 2021-08-27 | 陕西科技大学 | Preparation method of short fiber-based modified carbon fiber |
| CN114934387A (en) * | 2022-05-25 | 2022-08-23 | 中国科学院宁波材料技术与工程研究所 | High-thermal-conductivity carbon fiber and continuous preparation method |
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| CN102409528A (en) * | 2011-08-08 | 2012-04-11 | 哈尔滨工业大学 | Preparation method of carbon fiber reinforcement grafted by graphene oxide |
| CN103321036A (en) * | 2013-06-29 | 2013-09-25 | 西北工业大学 | Method for electrochemically modifying surface of ultrasonic-enhanced carbon fiber |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106192363A (en) * | 2016-08-11 | 2016-12-07 | 西北工业大学 | A kind of method of the surface modification of carbon fiber plasma grafting graphene oxide |
| CN106637923A (en) * | 2016-10-17 | 2017-05-10 | 哈尔滨工业大学 | Method of quickly and continuously depositing graphene on surface of electric-conductive fibers |
| CN109837740A (en) * | 2017-11-27 | 2019-06-04 | 四川东邦碳纤维材料有限公司 | A kind of surface treatment method of carbon fiber and the carbon fiber of preparation |
| CN108286187A (en) * | 2017-12-26 | 2018-07-17 | 山东大学 | A kind of preparation method of silane coupling agent auxiliary electrophoretic deposition initiated oxidation graphene modified carbon fiber |
| CN109750492A (en) * | 2018-12-20 | 2019-05-14 | 山东大学 | A kind of surface treatment method of carbon cloth surfaces homoepitaxial carbon nanotube early period |
| CN109733017A (en) * | 2019-01-03 | 2019-05-10 | 南京航空航天大学 | Containing graphene/resin/carbon fiber modifying electrothermal layer composite material, preparation method and use |
| CN110904774A (en) * | 2019-12-02 | 2020-03-24 | 哈尔滨学院 | Modular self-snow-melting pavement based on graphene |
| CN111675286A (en) * | 2020-06-01 | 2020-09-18 | 重庆三峡学院 | Modified carbon fiber cathode material, preparation method and application |
| CN113308882A (en) * | 2021-07-18 | 2021-08-27 | 陕西科技大学 | Preparation method of short fiber-based modified carbon fiber |
| CN114934387A (en) * | 2022-05-25 | 2022-08-23 | 中国科学院宁波材料技术与工程研究所 | High-thermal-conductivity carbon fiber and continuous preparation method |
| CN114934387B (en) * | 2022-05-25 | 2024-04-05 | 中国科学院宁波材料技术与工程研究所 | High-heat-conductivity carbon fiber and continuous preparation method |
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Application publication date: 20160622 |