CN116377705A - Electrochemical oxidation surface green high-efficiency modification method for carbon fiber fabric and resin-based composite material thereof - Google Patents
Electrochemical oxidation surface green high-efficiency modification method for carbon fiber fabric and resin-based composite material thereof Download PDFInfo
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 193
- 239000004744 fabric Substances 0.000 title claims abstract description 167
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 151
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 151
- 238000006056 electrooxidation reaction Methods 0.000 title claims abstract description 45
- 238000002715 modification method Methods 0.000 title claims abstract description 13
- 239000000805 composite resin Substances 0.000 title claims description 43
- 239000000463 material Substances 0.000 title claims description 40
- 229920005989 resin Polymers 0.000 claims abstract description 57
- 239000011347 resin Substances 0.000 claims abstract description 57
- 238000000034 method Methods 0.000 claims abstract description 49
- 230000008569 process Effects 0.000 claims abstract description 23
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 238000010301 surface-oxidation reaction Methods 0.000 claims description 48
- 239000000243 solution Substances 0.000 claims description 26
- 239000003292 glue Substances 0.000 claims description 24
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 16
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 16
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 16
- 239000001099 ammonium carbonate Substances 0.000 claims description 16
- 239000003792 electrolyte Substances 0.000 claims description 14
- 238000012986 modification Methods 0.000 claims description 13
- 230000004048 modification Effects 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 229920005992 thermoplastic resin Polymers 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 229920001187 thermosetting polymer Polymers 0.000 claims description 8
- 238000000748 compression moulding Methods 0.000 claims description 7
- 239000003822 epoxy resin Substances 0.000 claims description 7
- 229920000647 polyepoxide Polymers 0.000 claims description 7
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 5
- 239000004952 Polyamide Substances 0.000 claims description 5
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 229920002647 polyamide Polymers 0.000 claims description 5
- 229920002530 polyetherether ketone Polymers 0.000 claims description 5
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims description 4
- 238000007731 hot pressing Methods 0.000 claims description 4
- 238000003825 pressing Methods 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 239000002131 composite material Substances 0.000 abstract description 16
- 230000003647 oxidation Effects 0.000 abstract description 16
- 238000007254 oxidation reaction Methods 0.000 abstract description 16
- 239000003795 chemical substances by application Substances 0.000 abstract description 15
- 238000004513 sizing Methods 0.000 abstract description 13
- 239000011159 matrix material Substances 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 230000003746 surface roughness Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 20
- 239000000835 fiber Substances 0.000 description 14
- 230000006872 improvement Effects 0.000 description 14
- 238000002156 mixing Methods 0.000 description 9
- 229920002120 photoresistant polymer Polymers 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 3
- MUTGBJKUEZFXGO-UHFFFAOYSA-N hexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21 MUTGBJKUEZFXGO-UHFFFAOYSA-N 0.000 description 3
- 229920002239 polyacrylonitrile Polymers 0.000 description 3
- NFVPEIKDMMISQO-UHFFFAOYSA-N 4-[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC=C(O)C=C1 NFVPEIKDMMISQO-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000004643 cyanate ester Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- NZZFYRREKKOMAT-UHFFFAOYSA-N diiodomethane Chemical compound ICI NZZFYRREKKOMAT-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
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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
- D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
- C08J2363/02—Polyglycidyl ethers of bis-phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
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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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
The invention relates to the technical field of carbon fibers, in particular to an electrochemical oxidation surface green high-efficiency modification method of a carbon fiber fabric and a resin matrix composite material thereof. The untreated commercial carbon fiber fabric is used as the anode, so that only part of sizing agent is etched in the oxidation process, and the rest of sizing agent can play a certain role in protecting the carbon fiber fabric body in the subsequent electrochemical oxidation process, thereby increasing the surface roughness and the number of polar functional groups of the carbon fiber fabric without losing the mechanical properties of the carbon fiber fabric. The preparation method provided by the invention is simple, low in cost, stable in process, convenient and fast, and convenient for mass production.
Description
Technical Field
The invention relates to the technical field of carbon fibers, in particular to an electrochemical oxidation surface green efficient modification method of a carbon fiber fabric and a resin matrix composite material thereof.
Background
Carbon fiber is a novel fibrous carbon material with carbon content of more than 90%, and has been widely researched and developed because of its high temperature resistance, corrosion resistance, small thermal expansion coefficient, good dimensional stability, high specific strength, superior specific modulus, etc. However, carbon fibers are rarely used alone, and Carbon Fiber reinforced resin matrix Composites (CFRP) are generally prepared as reinforcements.
CFRP has the characteristics of light weight, easy molding, strong designability, excellent mechanical property and the like, is considered as one of the most potential structural materials, and is also a technological place for the competitive development of all countries of the world at present. CFRP, while having a range of excellent properties, has some unavoidable problems, most typically, as an anisotropic material, the excellent properties of carbon fiber composites are mainly concentrated in the axial direction of the fibers, without fiber reinforcement between layers and in the transverse direction, resulting in lower interlaminar shear strength and transverse tensile strength of the prepared composites. This phenomenon is mainly caused by: after pre-oxidation and high-temperature carbonization, the surface of the carbon fiber presents a disordered graphite structure, has fewer active functional groups, low surface energy, large inertia and smooth surface, so that the carbon fiber and a resin matrix are difficult to realize good infiltration and combination, and finally the reinforcing effect of the carbon fiber on the composite material cannot be fully exerted.
In order to promote the interfacial interaction between the carbon fiber and the resin matrix, a great deal of surface modification research is carried out to improve the mechanical properties of the composite material. The surface oxidation modification increases the number and roughness of active groups on the surface of the carbon fiber by roughening, activating and the like on the surface of the carbon fiber, so that the interface bonding strength between the carbon fiber and the resin is improved. In recent years, various treatment methods such as liquid phase oxidation, electrochemical anodic oxidation, plasma treatment, chemical grafting and the like are reported successively for surface modification of carbon fibers. The electrochemical anodic oxidation has the advantages of being suitable for continuous production, convenient and quick, easy to control parameters such as current and process, electrolyte system and the like, and becomes the most mature carbon fiber surface treatment method in the current industrial production technology. However, at present, the electrochemical oxidation treatment of the carbon fiber mainly aims at fiber filaments or fiber bundles, and is usually performed without sizing or removing sizing agent, so that the surface of the carbon fiber is excessively etched in the oxidation process, a large number of defects are generated on the surface of the carbon fiber, the structure of the fiber is damaged, and the strength of the carbon fiber is reduced. At present, electrochemical oxidation of the whole carbon fiber fabric is not reported. The direct electrochemical oxidation of the carbon fiber fabric can reduce the cost and production budget in the process of weaving the carbon fiber tows into the carbon fiber fabric, improve the efficiency of carbon fiber modification and provide convenience for the industrialized preparation of fiber resin matrix composite materials.
Disclosure of Invention
The invention provides an electrochemical oxidation surface green high-efficiency modification method of a carbon fiber fabric and a resin matrix composite thereof, which aim to avoid a great number of defects on the surface of the carbon fiber caused by excessive etching of the surface of the carbon fiber in the oxidation process of the carbon fiber and damage of the structure of the fiber.
The invention is realized by the following technical scheme: an electrochemical oxidation surface green high-efficiency modification method of a carbon fiber fabric comprises the following steps:
(1) Cutting the untreated carbon fiber fabric into a desired size;
(2) Weighing ammonium bicarbonate powder with certain mass, adding the ammonium bicarbonate powder into deionized water, and fully dissolving to obtain an aqueous solution with certain ammonium bicarbonate concentration to prepare an electrolyte;
(3) Immersing the cut carbon fiber fabric in the step (1) serving as an anode for electrochemical oxidation and a graphite plate serving as a cathode into the electrolyte prepared in the step (2);
(4) Adopting a constant voltage mode of a direct current power supply at room temperature, and carrying out electrochemical oxidation treatment on the carbon fiber fabric for a certain time under a certain voltage;
(5) Washing the treated carbon fiber fabric with deionized water to neutrality, and stoving to constant weight to obtain the electrochemical surface oxidation treated carbon fiber fabric with surface O/C increased by 1-17%, N/C increased by 78-184% and surface energy increased by 7-53%.
As a further improvement of the technical scheme of the modification method, the carbon fiber fabric is a continuous carbon fiber fabric of unidirectional cloth, biaxial cloth or woven cloth.
As a further improvement of the technical scheme of the modification method, in the step (2), the concentration of the ammonium bicarbonate in the electrolyte is 2-5wt%.
As a further improvement of the technical scheme of the modification method, in the step (4), the voltage in the constant voltage mode is 5-10V, and the electrochemical oxidation treatment time is 100-1000 s.
The invention further provides a preparation method of the resin composite material of the electrochemical surface oxidation modified carbon fiber fabric, which comprises the following steps:
(1) preparing a resin glue solution, and then placing the carbon fiber fabric subjected to electrochemical surface oxidation treatment, which is prepared by the method, in the prepared resin glue solution;
(2) and (3) layering the carbon fiber fabric soaked with the resin glue solution obtained in the step (1) on a die, and performing compression molding after reaching the required thickness to obtain the resin composite material of the electrochemical surface oxidation modified carbon fiber fabric.
As a further improvement of the technical scheme of the preparation method of the resin composite material, the resin in the resin glue solution is thermoplastic resin or thermosetting resin.
As a further improvement of the technical scheme of the preparation method of the resin composite material, the thermoplastic resin is polyamide, polyether-ether-ketone or polyphenylene sulfide.
As a further improvement of the technical scheme of the preparation method of the resin composite material, the process of the compression molding of the thermoplastic resin comprises the following steps: hot-pressing for 30min under 10MPa and a certain temperature, cold-pressing to normal temperature, and demoulding.
As a further improvement of the technical scheme of the preparation method of the resin composite material, the thermosetting resin is epoxy resin, vinyl resin or cyanate resin.
As a further improvement of the technical scheme of the preparation method of the resin composite material, the interlaminar shear strength of the resin composite material is improved by 10% -27% after electrochemical oxidation treatment.
Compared with the prior art, the invention has the following beneficial effects:
(1) At present, the surface treatment process of the carbon fiber fabric needs to firstly remove the sizing agent on the surface of the carbon fiber, which is unfavorable for the industrial application of the carbon fiber fabric, and the structure of the carbon fiber itself can be damaged in the process of removing the sizing agent and the oxidation treatment of the carbon fiber body, thereby reducing the strength of the carbon fiber fabric. In particular, the photoresist removing process requires a large amount of organic solvent, which not only significantly increases the cost and greatly prolongs the production period, but also deteriorates the production environment, and the treatment and discharge of the used organic solvent can cause serious environmental burden. The invention directly carries out surface oxidation modification on the carbon fiber fabric under the condition of not removing the sizing agent on the surface of the carbon fiber fabric, improves the number of surface active groups of the carbon fiber fabric, increases the surface roughness of the carbon fiber fabric, and increases the interface bonding performance between the carbon fiber fabric and the resin matrix on the premise of not damaging the self performance of the carbon fiber fabric.
(2) At present, most of carbon fiber modification researches mainly aim at carbon fiber filaments or carbon fiber bundles, which are not beneficial to industrialized popularization and application of carbon fibers. The invention directly carries out surface oxidation modification on the carbon fiber fabric, and has important significance for promoting the industrialized application of carbon fibers.
(3) The carbon fiber fabric can be directly used for preparing the resin matrix composite without subsequent treatment, and has the advantages of good repeatability and high performance stability.
(4) The electrolyte has the advantages of green and environment-friendly property and low cost; in addition, the electrochemical modification process is convenient and quick, and is convenient for large-scale production.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the invention and together with the description, serve to explain the principles of the invention.
In order to more clearly illustrate the embodiments of the invention or the technical solutions of the prior art, the drawings which are used in the description of the embodiments or the prior art will be briefly described, and it will be obvious to a person skilled in the art that other drawings can be obtained from these drawings without inventive effort.
FIG. 1 is a schematic view of an apparatus for electrochemical oxidation according to the present invention.
Fig. 2 is an SEM photograph of the non-degummed, electrochemically oxidized carbon fiber fabric (a) obtained in example 5 of the present invention and the degummed, electrochemically oxidized carbon fiber fabric (B) prepared in comparative example 1.
Fig. 3 is an SEM photograph of the resin composite interface (a) of the non-degummed electrochemical surface oxidation modified carbon fiber fabric obtained in example 10 of the present invention and the resin composite interface (B) of the degummed electrochemical oxidized carbon fiber fabric prepared in comparative example 3.
Detailed Description
In order that the above objects, features and advantages of the invention will be more clearly understood, a further description of the invention will be made. It should be noted that, without conflict, the embodiments of the present invention and features in the embodiments may be combined with each other.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced otherwise than as described herein; it will be apparent that the embodiments in the specification are only some, but not all, embodiments of the invention.
The performance test criteria of the embodiment of the invention are as follows:
1) Scanning Electron Microscope (SEM) photograph of the carbon fiber fabric after electrochemical oxidation: and taking a beam of carbon fiber fabric subjected to oxidation treatment, sticking the beam on a sample disc, then spraying metal, and testing by a scanning electron microscope (Hitachi SU 8010).
2) SEM photograph of the resin composite interface of the electrochemical surface oxidation modified carbon fiber fabric: the section of the carbon fiber resin composite material was stuck on a scanning disk, then subjected to metal spraying, and tested by a scanning electron microscope (HitachiSU 8010).
3) O/C, N/C ratio of carbon fiber fabric surface: and (3) testing by adopting X-ray photoelectron spectroscopy (XPS) and calculating to obtain the O/C, N/C ratio of the surface of the carbon fiber fabric. Taking a bundle of oxidized carbon fiber fabrics, using a 3M insulating double-sided tape to paste and fix the bundle onto a special sample stage for testing, putting the sample stage into an X-ray photoelectron spectrometer (Nexsa, thermoFisher Scientific, USA), and adopting an Al target (1486.6 eV) for testing, wherein the full spectrum passing energy is 150eV, and the step length is 1eV; the fine sweep spectrum energy is 50eV, and the step length is 0.1eV.
4) Surface energy of carbon fiber fabric: the surface energy of the carbon fiber fabrics was tested using a contact angle tester (DSA 100, germany). The contact angles of water and diiodomethane on the carbon fiber fabric are firstly measured respectively according to a biliquid method, and then the surface energy of the fiber is calculated by adopting an OWRK equation.
5) Monofilament tensile properties of carbon fiber fabrics were tested: according to GB/T31290-2014.
6) Interlaminar shear strength of carbon fiber fabric/resin composite: referring to GB/T30969, the interlaminar shear strength of carbon fiber fabric/resin composites was tested using the short beam bending method.
The invention provides a specific embodiment of an electrochemical oxidation surface green high-efficiency modification method of a carbon fiber fabric, which comprises the following steps:
(1) Cutting the untreated carbon fiber fabric into a desired size;
(2) Weighing ammonium bicarbonate powder with certain mass, adding the ammonium bicarbonate powder into deionized water, and fully dissolving to obtain an aqueous solution with certain ammonium bicarbonate concentration to prepare an electrolyte;
(3) Immersing the cut carbon fiber fabric in the step (1) serving as an anode for electrochemical oxidation and a graphite plate serving as a cathode into the electrolyte prepared in the step (2);
(4) Adopting a constant voltage mode of a direct current power supply at room temperature, and carrying out electrochemical oxidation treatment on the carbon fiber fabric for a certain time under a certain voltage;
(5) Washing the treated carbon fiber fabric with deionized water to neutrality, and stoving to constant weight to obtain the electrochemical surface oxidation treated carbon fiber fabric with surface O/C increased by 1-17%, N/C increased by 78-184% and surface energy increased by 7-53%.
In the present invention, the carbon fiber fabric used is a commercial carbon fiber fabric, and the carbon fiber fabric may be a continuous carbon fiber fabric of unidirectional cloth, biaxial cloth or woven cloth. The untreated commercial carbon fiber fabric is used as the anode, so that only part of sizing agent is etched in the oxidation process, and the rest of sizing agent can play a certain role in protecting the carbon fiber fabric body in the subsequent electrochemical oxidation process, thereby increasing the surface roughness and the number of polar functional groups of the carbon fiber fabric without losing the mechanical properties of the carbon fiber fabric. The preparation method provided by the invention is simple, low in cost, stable in process, convenient and fast, and convenient for mass production.
In one embodiment provided by the invention, in step (2), the concentration of ammonium bicarbonate in the electrolyte is 2-5wt%.
In another embodiment of the present invention, in step (4), the voltage in the constant voltage mode is 5-10V, and the electrochemical oxidation treatment time is 100 s-1000 s.
The invention further provides a preparation method of the resin composite material of the electrochemical surface oxidation modified carbon fiber fabric, which comprises the following steps:
(1) preparing a resin glue solution, and then placing the carbon fiber fabric subjected to electrochemical surface oxidation treatment, which is prepared by the method, in the prepared resin glue solution;
(2) and (3) layering the carbon fiber fabric soaked with the resin glue solution obtained in the step (1) on a die, and performing compression molding after reaching the required thickness to obtain the resin composite material of the electrochemical surface oxidation modified carbon fiber fabric.
In the invention, the resin in the resin glue solution is thermoplastic resin or thermosetting resin. Preferably, the thermoplastic resin comprises polyamide, polyether ether ketone, polyphenylene sulfide; the thermosetting resin comprises epoxy resin, vinyl resin and cyanate resin.
Specifically, the preparation method of the thermoplastic resin glue solution comprises the following steps: and dispersing polyamide, polyether-ether-ketone or polyphenylene sulfide powder in an ethanol solution, and uniformly mixing to obtain the thermoplastic resin glue solution.
Further, the method for preparing the resin glue solution by the thermosetting resin comprises the following steps: after uniformly mixing the epoxy resin E-51 and the curing agent cis-hexahydrophthalic anhydride (HHPA) according to the mass ratio of = 100:79.6, 0.5wt% of 2,4, 6-tri-carboxylic acid is added
(dimethylaminomethyl) phenol (DMP-30) and uniformly mixing to obtain resin glue solution; uniformly mixing vinyl resin, a small amount of accelerator and an initiator according to a certain proportion to obtain resin glue solution; the cyanate resin CE and the catalyst dibutyl tin dilaurate (DBTDL) are mixed according to the mass ratio of 1: and (3) uniformly mixing the components to obtain the resin glue solution.
Further, the compression molding process comprises the following steps: 1) Thermoplastic resin system: the polyamide, polyether-ether-ketone and polyphenylene sulfide are subjected to compression molding respectively under the conditions of 10MPa and 240 ℃ for 30min, cold-pressed to normal temperature and then demoulded; hot-pressing at 390 ℃ under 10MPa for 30min, cold-pressing to normal temperature, and demoulding; hot-pressing at 300 ℃ under 10MPa for 30min, cold-pressing to normal temperature, and demoulding.
2) Thermosetting resin system:
epoxy resin system: solidifying for 1h at 100 ℃ under 0MPa, solidifying for 2h at 140 ℃ under 15MPa, cooling for 6h, and demoulding; vinyl resin system: solidifying for 2 hours at 0MPa and 90 ℃, then solidifying for 2 hours at 5MPa and 110 ℃, then solidifying for 4 hours at 10MPa and 130 ℃, cooling for 6 hours, and demoulding; cyanate ester resin system: solidifying at 90 deg.C and 0.5 hr under 0MPa, solidifying at 120 deg.C and 5MPa for 2 hr, solidifying at 140 deg.C and 10MPa for 3 hr, cooling for 6 hr, demoulding.
Further, after electrochemical oxidation treatment, the interlaminar shear strength of the resin composite material is improved by 10% -27%.
Specific embodiments of the present invention are described in detail below.
Example 1
An electrochemical oxidation surface green high-efficiency modification method of a carbon fiber fabric comprises the following steps:
(1) Untreated polyacrylonitrile-based carbon fiber unidirectional fabric (monofilament tensile strength of 4.89GPa; surface energy of 35.56 mJ/m) 2 The method comprises the steps of carrying out a first treatment on the surface of the Surface oxygen content 19.85%, carbon content 79.01%, N content 1.14%, O/c=0.251, N/c=0.014) was cut to a size of 10 x 8 cm.
(2) 25g of ammonium bicarbonate powder was weighed and mixed with 800g of deionized water to prepare an aqueous solution with an ammonium bicarbonate concentration of 3.03wt%, which was the electrolyte.
(3) Immersing the carbon fiber fabric cut in the step (1) serving as an anode for electrochemical oxidation and a graphite plate serving as a cathode into the electrolyte prepared in the step (2).
(4) And (3) oxidizing the carbon fiber fabric for 1000s under the condition of 5V by adopting a constant voltage mode of a direct current power supply at room temperature.
(5) And washing the treated carbon fiber fabric with deionized water to be neutral, and drying the carbon fiber fabric to be constant weight to obtain the carbon fiber fabric subjected to electrochemical surface oxidation treatment.
The obtained carbon fiber fabric subjected to electrochemical surface oxidation treatment has the monofilament tensile strength of 4.34GPa, which is reduced by 11.24% compared with unmodified carbon fiber fabric; surface O/C is 0.269, which is improved by 7.17% compared with unmodified surface O/C; the N/C of the surface is 0.028, which is improved by 99.31 percent compared with the unmodified surface; surface energy of 48.68mJ/m 2 The improvement is 36.89% compared with the unmodified one.
Example 2
The method for modifying the electrochemical oxidation surface of the carbon fiber fabric in green and high efficiency has the same steps as in the embodiment 1, except that the constant voltage of the direct current power supply in the step (4) is 7V.
The obtained surface oxidation modified carbon fiber fabric has the monofilament tensile strength of 4.05GPa, which is reduced by 17.17% compared with the unmodified carbon fiber fabric; surface O/C is 0.289, which is 15.13% higher than unmodified; surface N/C is 0.032, which is 122.22% higher than that of unmodified surface; surface energy of 50.36mJ/m 2 The product is improved by 41.22% compared with the unmodified product.
Example 3
The method for modifying the electrochemical oxidation surface of the carbon fiber fabric in green and high efficiency has the same steps as in the embodiment 1, except that the constant voltage of the direct current power supply in the step (4) is 10V.
The obtained surface oxidation modified carbon fiber fabric has the monofilament tensile strength of 3.54GPa, which is reduced by 27.60 percent compared with the unmodified carbon fiber fabric; the surface O/C is 0.295, which is improved by 17.53% compared with the unmodified surface; surface N/C is 0.041, which is improved by 184.72% compared with unmodified surface N/C; surface energy of 54.50mJ/m 2 The product is improved by 53.26% compared with the unmodified product.
Example 4
The method for modifying the electrochemical oxidation surface of the carbon fiber fabric in green and high efficiency has the same steps as in the embodiment 3, except that the oxidation time in the step (4) is 100s.
The obtained surface oxidation modified carbon fiber fabric has the monofilament tensile strength of 4.72GPa, which is reduced by 3.47% compared with the unmodified carbon fiber fabric; surface O/C is 0.254, which is improved by 1.19% compared with unmodified surface O/C; surface N/C is 0.025, which is 78.57% higher than that of unmodified surface; surface energy of 38.14mJ/m 2 The improvement is 7.25% compared with the unmodified one.
Example 5
The method for modifying the electrochemical oxidation surface of the carbon fiber fabric in green and high efficiency has the same steps as in the embodiment 1, except that the oxidation time in the step (4) is 200s.
The obtained surface oxidation modified carbon fiber fabric has the monofilament tensile strength of 4.68GPa, which is reduced by 4.29 percent compared with the unmodified carbon fiber fabric; surface O/C is 0.278, which is improved by 10.75% compared with unmodified surface O/C; surface N/C is 0.040, which is 177.08% higher than unmodifiedThe method comprises the steps of carrying out a first treatment on the surface of the Surface energy of 44.09mJ/m 2 The improvement is 23.99% compared with the unmodified one.
Example 6
The method for modifying the electrochemical oxidation surface of the carbon fiber fabric in green and high efficiency has the same steps as in the embodiment 1, except that the oxidation time in the step (4) is 300s.
The obtained surface oxidation modified carbon fiber fabric has the monofilament tensile strength of 4.52GPa, which is 7.57 percent lower than that of unmodified carbon fiber fabric; surface O/C is 0.258, which is improved by 2.78% compared with unmodified surface O/C; surface N/C is 0.037, which is 157.64% higher than unmodified; surface energy of 48.76mJ/m 2 The improvement is 37.12% compared with the unmodified one.
Example 7
The method for modifying the electrochemical oxidation surface of the carbon fiber fabric in green and high efficiency has the same steps as in the embodiment 1, except that the oxidation time in the step (4) is 400s.
The obtained surface oxidation modified carbon fiber fabric has the monofilament tensile strength of 4.41GPa, which is reduced by 9.81 percent compared with the unmodified carbon fiber fabric; the surface O/C is 0.261, which is improved by 3.98 percent compared with the unmodified surface O/C; surface N/C is 0.034, which is 135.42% higher than unmodified; the surface energy was 51.59mJ/m 2 The improvement is 45.08% compared with the unmodified one.
Example 8
The method for modifying the electrochemical oxidation surface of the carbon fiber fabric in green and high efficiency has the same steps as in the embodiment 1, except that the oxidation time in the step (4) is 600s.
The obtained surface oxidation modified carbon fiber fabric has the monofilament tensile strength of 3.95GPa, which is reduced by 19.22% compared with the unmodified carbon fiber fabric; surface O/C is 0.279, which is improved by 11.15% compared with unmodified surface O/C; surface N/C is 0.035, which is 140.27% higher than that of unmodified surface; surface energy of 53.68mJ/m 2 The product is improved by 50.96% compared with the unmodified product.
Comparative example 1
The green and efficient modification method for the electrochemical oxidation surface of the carbon fiber fabric after the photoresist removal comprises the following steps:
(1) The same polyacrylonitrile-based carbon fiber unidirectional fabric as in example 1 is cut into a size of 10 x 8cm, soaked in acetone, ultrasonically cleaned by deionized water after 48 hours, and dried in an oven to constant weight, thereby obtaining the carbon fiber fabric after sizing agent removal.
(2) 25g of ammonium bicarbonate powder was weighed and mixed with 800g of deionized water to prepare an aqueous solution having a concentration of 3.03wt% ammonium bicarbonate.
(3) Immersing the carbon fiber fabric cut in the step (1) serving as an anode for electrochemical oxidation and a graphite plate serving as a cathode into the electrolyte prepared in the step (2).
(4) And (3) oxidizing the carbon fiber fabric for 100s under the condition of 10V by adopting a constant voltage mode of a direct current power supply at room temperature.
(5) And washing the treated carbon fiber fabric with deionized water to be neutral, and drying the carbon fiber fabric to be constant weight to obtain the oxidized modified carbon fiber fabric after the photoresist is removed.
The obtained carbon fiber fabric with the surface oxidized and modified after the photoresist removal has the monofilament tensile strength of 4.33GPa, which is reduced by 11.45 percent compared with the unmodified carbon fiber fabric; surface O/C is 0.359, which is 43.03% higher than unmodified; surface N/C is 0.053, which is improved by 278.57% compared with unmodified surface N/C; surface energy of 44.58mJ/m 2 The improvement is 27.37% compared with the unmodified one.
Comparative example 2
A resin composite material of a carbon fiber fabric with an unoxidized surface is mainly prepared by the following steps:
(1) Mixing epoxy resin E-51 and curing agent HHPA according to the mass ratio of = 100:79.6, then adding 0.5w% of DMP-30 and uniformly mixing to obtain resin glue solution;
(2) The same polyacrylonitrile-based carbon fiber fabric as in example 1 was directly placed in the prepared resin glue solution;
(3) And (3) paving the surface non-oxidized modified carbon fiber fabric soaked in the resin glue solution obtained in the step (2) on a die, putting the die into a hot press after the thickness is 2mm, solidifying for 1h at 0MPa and 100 ℃, pressurizing to 15MPa, heating to 140 ℃ for solidifying for 2h, and finally cooling for 6h to obtain the surface non-oxidized modified carbon fiber resin composite material.
The prepared resin composite material with the surface of the carbon fiber fabric not oxidized has the volume fraction of 64.43 percent, the tensile strength of 1578.64MPa and the interlaminar shear strength of 62.28MPa.
Example 9
A resin composite material adopting electrochemical surface oxidation to modify carbon fiber fabrics mainly comprises the following preparation processes:
(1) Mixing epoxy resin E-51 and curing agent HHPA according to the mass ratio of = 100:79.6, then adding 0.5w% of DMP-30 and uniformly mixing to obtain resin glue solution;
(2) Placing the electrochemical surface oxidation modified carbon fiber fabric prepared in the example 4 in the prepared resin glue solution;
(3) And (3) paving the carbon fiber fabric soaked with the resin glue solution obtained in the step (2) on a die, putting the die into a hot press after the thickness is 2mm, solidifying for 1h at the temperature of 0MPa and 100 ℃, pressurizing to 15MPa, heating to 140 ℃ and solidifying for 2h, and finally cooling for 6h to obtain the carbon fiber resin composite material.
The prepared resin composite material of the electrochemical surface oxidation modified carbon fiber fabric has the volume fraction of 64.43 percent; tensile strength is 1658.49MPa, and is improved by 5.06% compared with comparative example 2; the interlaminar shear strength of the carbon fiber composite material is 68.72MPa, and is improved by 10.34% compared with comparative example 2.
Example 10
The process was exactly the same as in example 9, except that the electrochemical surface oxidation modified carbon fiber fabric prepared in example 5 was used.
The prepared resin composite material of the electrochemical surface oxidation modified carbon fiber fabric has the volume fraction of 64.43 percent; the tensile strength is 1735.43MPa, which is improved by 9.94% compared with comparative example 2; the interlaminar shear strength of the carbon fiber composite material is 79.29MPa, and is improved by 27.31% compared with comparative example 2.
Example 11
The process was exactly the same as in example 9, except that the electrochemical surface oxidation modified carbon fiber fabric prepared in example 6 was used.
The prepared resin composite material of the electrochemical surface oxidation modified carbon fiber fabric has the volume fraction of 64.43 percent; the tensile strength is 1684.16MPa, which is improved by 6.71% compared with comparative example 2; the interlaminar shear strength of the carbon fiber composite material is 75.08MPa, which is improved by 20.54% compared with comparative example 2.
Example 12
The process was exactly the same as in example 9, except that the electrochemical surface oxidation modified carbon fiber fabric prepared in example 7 was used.
The prepared resin composite material of the electrochemical surface oxidation modified carbon fiber fabric has the volume fraction of 64.43 percent; tensile strength is 1657.28MPa, and is improved by 5.01% compared with comparative example 2; the interlaminar shear strength of the carbon fiber composite material is 71.37MPa, which is improved by 14.59% compared with comparative example 2.
Example 13
The process was exactly the same as in example 9, except that the electrochemical surface oxidation modified carbon fiber fabric prepared in example 8 was used.
The prepared resin composite material of the electrochemical surface oxidation modified carbon fiber fabric has the volume fraction of 64.43 percent; tensile strength is 1589.91MPa, and is improved by 0.71% compared with comparative example 2; the interlaminar shear strength of the carbon fiber composite material is 71.01MPa, which is improved by 14.02% compared with comparative example 2.
Comparative example 3
The process was exactly the same as in example 9 except that the post-photoresist-removal electrochemical surface oxidation modified carbon fiber fabric prepared in comparative example 1 was used.
The prepared resin composite material of the electrochemical surface oxidation modified carbon fiber fabric after the photoresist removal has the volume fraction of 64.43 percent; the tensile strength is 1618.26MPa, which is improved by 2.51 percent compared with comparative example 2 and is reduced by 2.43 percent compared with example 9; the interlaminar shear strength of the carbon fiber composite material is 75.31MPa, which is improved by 20.92% compared with comparative example 2 and 9.59% compared with example 9.
The tensile strength of the resin composite material of the electrochemical surface oxidation modified carbon fiber fabric prepared in the embodiment 10 of the invention can be improved by 7.24% compared with that of the resin composite material of the electrochemical surface oxidation modified carbon fiber fabric prepared in the comparative example 3 after photoresist removal, and the interlayer shear strength can be improved by 5.28% compared with that of the comparative example 3. The invention is fully shown that the surface of the carbon fiber fabric is directly subjected to surface oxidation modification under the condition of not removing the sizing agent, so that the method is simpler and environment-friendly than the prior process of re-modifying after removing the sizing agent, and the performance of the resin composite material prepared by the modified carbon fiber fabric is better.
As can be seen from fig. 2, after the electrochemical oxidation treatment, it is obvious that the sizing agent layer on the surface of the non-gummed electrochemical oxidized carbon fiber fabric is partially detached, and the structure of the fiber is partially exposed, so that the roughness of the fiber surface is increased. After the gel is removed, SEM of the carbon fiber fabric has obvious gully structure, and the electrochemical oxidation causes certain etching to the fiber.
As can be seen from fig. 3, after the electrochemical oxidation treatment, the resin part remains on the surface of the fiber at the time of fracture of the composite material, which is an expression that the bonding force between the fiber and the resin becomes strong. Compared with the resin composite material of the gel-removed electrochemical oxidation carbon fiber fabric, more resin remains on the section of the resin composite material of the non-gel-removed electrochemical oxidation carbon fiber fabric, which indicates that the oxidation effect of the electrochemical oxidation on the commercial carbon fiber fabric enables the interface between the fiber and the resin to be better improved.
The foregoing is only a specific embodiment of the invention to enable those skilled in the art to understand or practice the invention. Although described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the embodiments, and they should be construed as covering the scope of the appended claims.
Claims (10)
1. The green and efficient modification method for the electrochemical oxidation surface of the carbon fiber fabric is characterized by comprising the following steps of:
(1) Cutting the untreated carbon fiber fabric into a desired size;
(2) Weighing ammonium bicarbonate powder with certain mass, adding the ammonium bicarbonate powder into deionized water, and fully dissolving to obtain an aqueous solution with certain ammonium bicarbonate concentration to prepare an electrolyte;
(3) Immersing the cut carbon fiber fabric in the step (1) serving as an anode for electrochemical oxidation and a graphite plate serving as a cathode into the electrolyte prepared in the step (2);
(4) Adopting a constant voltage mode of a direct current power supply at room temperature, and carrying out electrochemical oxidation treatment on the carbon fiber fabric for a certain time under a certain voltage;
(5) And washing the treated carbon fiber fabric to be neutral by deionized water, and then drying to constant weight to obtain the carbon fiber fabric subjected to electrochemical surface oxidation treatment, wherein the O/C ratio of the surface of the carbon fiber fabric is improved by 1% -17% compared with that of the carbon fiber fabric not subjected to electrochemical surface oxidation treatment, the N/C ratio is improved by 78% -184%, and the surface energy is improved by 7% -53%.
2. The method for the green and efficient modification of the electrochemically oxidized surface of a carbon fiber fabric according to claim 1, wherein the carbon fiber fabric is a continuous carbon fiber fabric of unidirectional cloth, biaxial cloth or woven cloth.
3. The method for green and efficient modification of an electrochemically oxidized surface of a carbon fiber fabric according to claim 1, wherein in the step (2), the concentration of ammonium bicarbonate in the electrolyte is 2-5wt%.
4. The method for green and efficient modification of the electrochemical oxidation surface of a carbon fiber fabric according to claim 1, wherein in the step (4), the voltage in the constant voltage mode is 5-10V, and the electrochemical oxidation treatment time is 100 s-1000 s.
5. The preparation method of the resin composite material of the electrochemical surface oxidation modified carbon fiber fabric is characterized by comprising the following steps:
(1) preparing a resin glue solution, and then placing the carbon fiber fabric subjected to electrochemical surface oxidation treatment, which is prepared by the method of any one of claims 1 to 4, in the prepared resin glue solution;
(2) and (3) layering the carbon fiber fabric soaked with the resin glue solution obtained in the step (1) on a die, and performing compression molding after reaching the required thickness to obtain the resin composite material of the electrochemical surface oxidation modified carbon fiber fabric.
6. The method for preparing a resin composite material for electrochemical surface oxidation modified carbon fiber fabrics according to claim 5, wherein the resin in the resin glue solution is thermoplastic resin or thermosetting resin.
7. The method for preparing a resin composite material for electrochemical surface oxidation modified carbon fiber fabrics according to claim 5, wherein the thermoplastic resin is polyamide, polyether ether ketone or polyphenylene sulfide.
8. The method for preparing the resin composite material of the electrochemical surface oxidation modified carbon fiber fabric according to claim 6, wherein the process of compression molding the thermoplastic resin is as follows: 10 Hot-pressing for 30min under the condition of MPa and a certain temperature, cold-pressing to normal temperature, and demoulding.
9. The method for preparing a resin composite material for electrochemical surface oxidation modified carbon fiber fabrics according to claim 5, wherein the thermosetting resin is epoxy resin, vinyl resin or cyanate resin.
10. The method for preparing the resin composite material of the electrochemical surface oxidation modified carbon fiber fabric, which is characterized in that after electrochemical oxidation treatment, the interlaminar shear strength of the resin composite material is improved by 10% -27%.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101560727A (en) * | 2009-05-13 | 2009-10-21 | 北京化工大学 | Method for preparing high-performance carbon fibers |
| CN107385896A (en) * | 2017-07-05 | 2017-11-24 | 北京航空航天大学 | A kind of organic matter immersion and the method for electrochemicial oxidation carbon fiber |
| CN107964217A (en) * | 2017-12-14 | 2018-04-27 | 郑州四维特种材料有限责任公司 | A kind of carbon fibre reinforced composite resin matrix, carbon fibre reinforced composite and preparation method thereof, base plate of ping-pong bat |
| CN108755126A (en) * | 2018-05-08 | 2018-11-06 | 中国科学院宁波材料技术与工程研究所 | The method and carbon fibre composite of electrochemical polymerization modified surface Treatment of Carbon |
| CN109208320A (en) * | 2018-07-12 | 2019-01-15 | 北京化工大学 | A kind of surface treatment method of dry-jet wet-spinning carbon fiber |
| CN110706942A (en) * | 2018-07-10 | 2020-01-17 | 中国科学院上海硅酸盐研究所 | Method for modifying carbon material through electrochemical oxidation |
| CN111534050A (en) * | 2020-05-27 | 2020-08-14 | 北京化工大学 | Carbon fiber composite material with multi-scale high-temperature-resistant interface structure and preparation method thereof |
| TR2022011520A2 (en) * | 2022-07-19 | 2022-08-22 | Univ Yildiz Teknik | AN ELECTROCHEMICAL GREEN SURFACE TREATMENT METHOD FOR THE USE OF CARBON FIBERS AS ADVANCED MATERIAL |
-
2023
- 2023-04-07 CN CN202310362267.4A patent/CN116377705A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101560727A (en) * | 2009-05-13 | 2009-10-21 | 北京化工大学 | Method for preparing high-performance carbon fibers |
| CN107385896A (en) * | 2017-07-05 | 2017-11-24 | 北京航空航天大学 | A kind of organic matter immersion and the method for electrochemicial oxidation carbon fiber |
| CN107964217A (en) * | 2017-12-14 | 2018-04-27 | 郑州四维特种材料有限责任公司 | A kind of carbon fibre reinforced composite resin matrix, carbon fibre reinforced composite and preparation method thereof, base plate of ping-pong bat |
| CN108755126A (en) * | 2018-05-08 | 2018-11-06 | 中国科学院宁波材料技术与工程研究所 | The method and carbon fibre composite of electrochemical polymerization modified surface Treatment of Carbon |
| CN110706942A (en) * | 2018-07-10 | 2020-01-17 | 中国科学院上海硅酸盐研究所 | Method for modifying carbon material through electrochemical oxidation |
| CN109208320A (en) * | 2018-07-12 | 2019-01-15 | 北京化工大学 | A kind of surface treatment method of dry-jet wet-spinning carbon fiber |
| CN111534050A (en) * | 2020-05-27 | 2020-08-14 | 北京化工大学 | Carbon fiber composite material with multi-scale high-temperature-resistant interface structure and preparation method thereof |
| TR2022011520A2 (en) * | 2022-07-19 | 2022-08-22 | Univ Yildiz Teknik | AN ELECTROCHEMICAL GREEN SURFACE TREATMENT METHOD FOR THE USE OF CARBON FIBERS AS ADVANCED MATERIAL |
Non-Patent Citations (9)
| Title |
|---|
| 余木火 等: "粘胶基碳纤维连续式电化学氧化表面处理(1)——碳纤维表面的物理化学性能", 玻璃钢/复合材料, no. 01, 31 January 2000 (2000-01-31), pages 23 - 27 * |
| 余木火, 赵世平, 滕翠青, 韩克清, 余奇平, 顾丽霞: "粘胶基碳纤维连续式电化学氧化表面处理(1)――碳纤维表面的物理化学性能", 玻璃钢/复合材料, no. 01, 28 January 2000 (2000-01-28) * |
| 季春晓;常丽;周新露;李昌俊;: "聚丙烯腈基碳纤维电化学氧化表面处理研究", 石油化工技术与经济, no. 05, 25 October 2013 (2013-10-25) * |
| 房宽峻 等: "不同电化学条件下氧化后碳纤维表面基团的XPS分析", 青岛大学学报(自然科学版), vol. 29, no. 04, 31 December 1998 (1998-12-31), pages 16 - 23 * |
| 房宽峻, 蔡玉青, 戴瑾瑾, 王菊生: "电解质浓度对电化学氧化后碳纤维表面基团含量的影响", 青岛大学学报(工程技术版), no. 01, 28 February 1999 (1999-02-28) * |
| 朱泉, 吴婵娟, 戴瑾瑾: "电化学氧化对粘胶基碳纤维表面性质的影响研究", 纺织学报, no. 03, 20 June 1997 (1997-06-20) * |
| 李国明;刘钟铃;易明;史有好;: "国产碳纤维表面性能研究", 高科技纤维与应用, no. 02, 30 April 2013 (2013-04-30) * |
| 胡郁菲;张雪娜;王彪;: "不同电流密度电化学处理对碳纤维表面结构及其界面性能的影响", 东华大学学报(自然科学版), no. 01, 15 February 2017 (2017-02-15) * |
| 郭云霞, 刘杰, 梁节英: "电化学改性对PAN基碳纤维表面状态的影响", 复合材料学报, no. 03, 30 June 2005 (2005-06-30) * |
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