CN114806079B - Preparation method of graphite/epoxy resin composite material - Google Patents
Preparation method of graphite/epoxy resin composite material Download PDFInfo
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- CN114806079B CN114806079B CN202210023197.5A CN202210023197A CN114806079B CN 114806079 B CN114806079 B CN 114806079B CN 202210023197 A CN202210023197 A CN 202210023197A CN 114806079 B CN114806079 B CN 114806079B
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- graphite
- epoxy resin
- composite material
- skeleton
- preform
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 173
- 239000002131 composite material Substances 0.000 title claims abstract description 83
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 77
- 239000010439 graphite Substances 0.000 title claims abstract description 77
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 68
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 41
- 239000004917 carbon fiber Substances 0.000 claims abstract description 41
- 238000007747 plating Methods 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 35
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052802 copper Inorganic materials 0.000 claims abstract description 32
- 239000010949 copper Substances 0.000 claims abstract description 32
- 230000008569 process Effects 0.000 claims abstract description 24
- 235000015895 biscuits Nutrition 0.000 claims abstract description 14
- 238000011282 treatment Methods 0.000 claims abstract description 11
- 239000002002 slurry Substances 0.000 claims abstract description 10
- 238000007639 printing Methods 0.000 claims abstract description 8
- 238000000110 selective laser sintering Methods 0.000 claims abstract description 8
- 238000005516 engineering process Methods 0.000 claims abstract description 7
- 238000010000 carbonizing Methods 0.000 claims abstract description 4
- 238000005470 impregnation Methods 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 39
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 29
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 28
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 24
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 23
- 239000005011 phenolic resin Substances 0.000 claims description 23
- 229920001568 phenolic resin Polymers 0.000 claims description 23
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- 238000009713 electroplating Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000002253 acid Substances 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 17
- 239000000654 additive Substances 0.000 claims description 17
- 230000000996 additive effect Effects 0.000 claims description 17
- 238000003763 carbonization Methods 0.000 claims description 15
- 239000011734 sodium Substances 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 13
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 12
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 12
- 238000004321 preservation Methods 0.000 claims description 12
- -1 polydithio-dipropyl Polymers 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 238000011049 filling Methods 0.000 claims description 10
- 230000007935 neutral effect Effects 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 229920001187 thermosetting polymer Polymers 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 238000007602 hot air drying Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000007569 slipcasting Methods 0.000 claims description 7
- 238000000465 moulding Methods 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical group [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 5
- RIRXDDRGHVUXNJ-UHFFFAOYSA-N [Cu].[P] Chemical compound [Cu].[P] RIRXDDRGHVUXNJ-UHFFFAOYSA-N 0.000 claims description 5
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 5
- 239000012964 benzotriazole Substances 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 5
- 238000005282 brightening Methods 0.000 claims description 4
- 238000000280 densification Methods 0.000 claims description 4
- 239000011812 mixed powder Substances 0.000 claims description 4
- 238000005086 pumping Methods 0.000 claims description 4
- 239000000080 wetting agent Substances 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 3
- 238000005087 graphitization Methods 0.000 claims description 3
- 238000007711 solidification Methods 0.000 claims description 3
- 230000008023 solidification Effects 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 claims description 2
- 230000000149 penetrating effect Effects 0.000 claims 1
- 239000011159 matrix material Substances 0.000 abstract description 15
- 238000013329 compounding Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- 238000004891 communication Methods 0.000 abstract description 2
- 238000009413 insulation Methods 0.000 description 37
- 238000005452 bending Methods 0.000 description 19
- 238000012360 testing method Methods 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000000428 dust Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000013212 metal-organic material Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- 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
- C08K9/02—Ingredients treated with inorganic substances
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
- B29C39/02—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor for making articles of definite length, i.e. discrete articles
- B29C39/10—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor for making articles of definite length, i.e. discrete articles incorporating preformed parts or layers, e.g. casting around inserts or for coating articles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/10—Processes of additive manufacturing
- B29C64/141—Processes of additive manufacturing using only solid materials
- B29C64/153—Processes of additive manufacturing using only solid materials using layers of powder being selectively joined, e.g. by selective laser sintering or melting
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/30—Auxiliary operations or equipment
- B29C64/379—Handling of additively manufactured objects, e.g. using robots
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C69/00—Combinations of shaping techniques not provided for in a single one of main groups B29C39/00 - B29C67/00, e.g. associations of moulding and joining techniques; Apparatus therefore
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y40/00—Auxiliary operations or equipment, e.g. for material handling
- B33Y40/20—Post-treatment, e.g. curing, coating or polishing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
-
- 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
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
-
- 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
- C08J5/10—Reinforcing macromolecular compounds with loose or coherent fibrous material characterised by the additives used in the polymer mixture
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
-
- 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
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
Abstract
The invention discloses a preparation method of a graphite/epoxy resin composite material, which comprises the following basic process links of rapidly printing a porous graphite skeleton biscuit by utilizing a selective laser sintering forming technology, carbonizing, carrying out multiple vacuum pressure impregnation, graphitizing, overall surface copper plating and other post-treatments on the porous graphite skeleton biscuit to obtain a high-conductivity porous graphite skeleton preform, pouring epoxy resin matrix slurry reinforced by chopped carbon fibers into a mold, compounding with a copper-plated porous graphite skeleton, and completely curing to obtain the graphite/epoxy resin composite material. The graphite/epoxy resin composite material provided by the invention has the advantages of environmental protection, rapidness, high efficiency and low cost, has good electric conduction, heat conduction and mechanical properties, and the comprehensive properties can be actively regulated and controlled by changing the porous graphite framework structure, so that the composite material has wide application prospects in the fields of communication engineering and electronic instruments and meters.
Description
Technical Field
The invention relates to a novel graphite/epoxy resin composite material and a preparation method thereof, in particular to a novel graphite/epoxy resin composite material rapid preparation method with high heat conduction, high electric conduction and excellent mechanical properties.
Technical Field
The polymer composite material has the comprehensive advantages of light weight, high strength, corrosion resistance, acid and alkali resistance, salt fog resistance, aging resistance, impact resistance, environmental suitability and the like, and the polymer composite material is gradually accepted by vast scientific and technological workers instead of metal materials. Graphite is used as a high heat-conducting and electric-conducting filler, and is compounded with various organic matters, so that the graphite is widely applied to industrial production and practical use. When graphite is used as a filler to prepare the organic compound material, the conductive property, the heat-conductive property and the mechanical property of the graphite are superior or not, and depend on the type, the quantity, the size, the arrangement and combination mode and the interaction of the graphite and an organic material matrix.
The epoxy resin and the phenolic resin are respectively filled and modified by adopting natural crystalline flake graphite at Sun Xiaosheng, liu Hongbo and the like of Hunan university, so that the graphite/resin heat conduction composite material is prepared, and the graphite/resin heat conduction composite material has higher heat conduction performance. It was found that as the mass fraction of graphite increased, the thermal conductivity of both the graphite/epoxy composite and the graphite/phenolic composite increased. The thermal conductivity increases faster at 15% -45% by mass of graphite, after which the rate of increase is slowed down; the compressive strength of the graphite/epoxy resin composite material is firstly increased and then decreased, and is smaller than that of pure epoxy resin without graphite, and the compressive strength of the graphite/phenolic resin-based heat-conducting composite material is continuously decreased. When the graphite/organic matter composite material is prepared by adopting the traditional process methods such as dry mixing or wet mixing, heating and pressing forming, because the graphite powder is only randomly, irregularly and discontinuously distributed in the organic matter matrix, when the adding amount of the graphite is small, the graphite powder is less in contact with each other, the quantity of heat conduction channels is less, the heat conduction performance is poor, and a three-dimensional heat conduction network can be spontaneously formed in the matrix only when the adding amount of the graphite powder exceeds a certain permeability threshold value, so that the heat conduction performance of the graphite/organic matter composite material is rapidly increased. However, excessive addition of graphite powder can cause damage to the organic matrix, resulting in reduced mechanical properties of the composite material, and in addition, the thermal conductivity of the composite material is very limited due to the presence of a large amount of thermal contact resistance between graphite powders.
Disclosure of Invention
The invention aims to provide a novel graphite/epoxy resin composite material and a preparation method thereof, which realize the cooperation of multiple technical targets such as high heat conduction, high electric conduction, excellent mechanical properties and the like. The present invention achieves the above object by: the novel graphite/epoxy resin composite material consists of a chopped carbon fiber reinforced epoxy resin matrix and a three-dimensional porous copper-plated graphite skeleton embedded therein, wherein the three-dimensional porous graphite skeleton is completely wrapped by a copper alloy and the chopped carbon fiber reinforced epoxy resin matrix, the three-dimensional porous copper-plated graphite skeleton is formed by interlacing interconnected pore systems and a plurality of controllable graphite heat conduction passages, and the volume ratio of the three-dimensional porous copper-plated graphite skeleton in the composite material is not higher than 50%. The preparation method of the graphite/epoxy resin composite material comprises the following process links of rapidly printing a three-dimensional porous graphite skeleton biscuit by utilizing a selective laser sintering molding technology, carbonizing, carrying out multiple vacuum pressure impregnation, graphitizing and other post-treatments on the three-dimensional porous graphite skeleton biscuit to obtain a high-heat-conductivity porous graphite network skeleton preform, carrying out integral copper plating treatment on the porous graphite network skeleton preform, and finally compounding the chopped carbon fiber reinforced epoxy resin with the three-dimensional porous copper-plated graphite skeleton by utilizing a slip casting molding technology to obtain the novel graphite/epoxy resin composite material. Because the porous graphite skeleton mode is adopted to be compounded with the epoxy resin matrix, a three-dimensional interpenetrating network structure composite material is formed, thereby being beneficial to fully exerting the high heat and electricity conducting performance of graphite and exerting the excellent mechanical performance of the chopped carbon fiber reinforced epoxy resin matrix; the continuous three-dimensional porous graphite skeleton has the advantages of greatly reducing the number of contact interfaces and being beneficial to improving the heat conduction and electric conduction performance of the composite material. The quantity and the connection mode of the heat conduction passages in the epoxy resin matrix are completely controllable, which provides possibility for actively regulating and controlling the comprehensive performance of the composite material.
The preparation process of the novel graphite/epoxy resin composite material comprises the following steps:
(1) The natural crystalline flake graphite/thermosetting phenolic resin mixed powder is prepared, preferably, the natural crystalline flake graphite powder is 200-800 meshes, the mass fraction is 60-90%, and the carbon content is not less than 99%; 200-900 meshes of thermosetting phenolic resin powder, and 10-40% of thermosetting phenolic resin powder by mass fraction; adding the mixture into a dry ball mill, and mixing for 4-6 hours to obtain graphite/phenolic resin mixed powder.
(2) And rapidly printing the porous graphite skeleton prototype by utilizing a selective laser sintering molding technology to finish secondary solidification, thereby obtaining the porous graphite skeleton biscuit. The combination of the parameters of the selective laser sintering process is preferably as follows: laser power 12W-17W, filling rate 1300-190 mm s -1 Filling the space of 0.1-0.2mm, layering the thickness of 0.1-0.3mm, preheating the temperature to 40-60 ℃, and shaping by adopting a contour scanning mode.
The secondary curing process parameters are preferably as follows: heating to 80-90 deg.c from room temperature, maintaining for 5-15 min, heating to 120-130 deg.c, maintaining for 10-30 min, heating to 160-180 deg.c and maintaining for 10-30 min.
(3) And (5) carbonizing the porous graphite skeleton biscuit. The carbonization process parameter combinations are preferably as follows: firstly, vacuumizing a carbonization furnace to below 100Pa, and introducing argon or nitrogen with the purity of 99% from room temperature to 350 ℃ at the speed of 60 ℃/h to 150 ℃/h; heating to 600 ℃ at a speed of 30-120 ℃/h; finally, heating to 800 ℃ at 180-240 ℃ per hour, preserving heat for 30-60 minutes, and cooling to room temperature along with the furnace.
(4) And (5) impregnating phenolic resin liquid under vacuum pressure, and carrying out densification treatment. The combination of the dipping process parameters is preferably as follows: vacuum pumping is carried out to below 100Pa, phenolic resin solution with the mass concentration of 20-40% is immersed into the carbonized graphite skeleton preform under the pressure of 0.1-0.5MPa, then the carbonized graphite skeleton preform is dried in a hot air drying oven with the temperature lower than 100 ℃, and then secondary carbonization is carried out according to the step (3).
(5) Repeating the step (4) for 2-3 times to obtain the high-density porous graphite skeleton preform.
(6) And (5) graphitizing. The high temperature graphitization process parameters are preferably as follows: firstly, pumping the vacuum degree of a carbonization furnace to be lower than 100Pa, heating the furnace to 350 ℃ from room temperature at a heating rate of 60 ℃/h, introducing argon or nitrogen with purity higher than 99%, heating the furnace to 2000-2600 ℃ at a heating rate of 180 ℃/h-360 ℃/h, preserving heat for 1-2h, cooling the furnace to room temperature, and taking out the furnace to obtain the high-heat-conductivity high-electric-conductivity porous graphite skeleton preform.
(7) Copper plating is carried out on the surface of the porous graphite skeleton preform. The process parameters are preferably as follows: putting the graphite skeleton preform prepared in the step (6) into 20g/L sodium hydroxide solution, performing ultrasonic vibration for 5-10 min, removing surface dust and greasy dirt, taking out, and cleaning with deionized water to neutrality; placing into electroplating solution, electroplating with graphite preform as cathode and phosphor copper plate as anode in constant current mode for 30-60min with current density of 2.5X10-6.5X10 A.m -2 Taking out the plated part, washing the plated part with deionized water to be neutral, putting the plated part into a mixed solution of benzotriazole with the mass fraction of 1-5% and ethanol with the mass fraction of 95-99%, passivating for 15-30min, taking out the plated part, washing the plated part with deionized water to be neutral, and drying the plated part in a drying oven at 50 ℃ to obtain the copper-plated porous graphite skeleton preform.
The ratio of the electroplating solution is as follows: the electroplating solution is prepared by adding water into 20-40ml of sulfuric acid with the mass concentration of more than 98%, 80-120g of copper sulfate, 2-5ml of acetic acid and 5-15ml of sulfate acid copper plating additive, and preparing 1L of electroplating solution, wherein the sulfate acid copper plating additive is a mixed solution consisting of a brightening agent, a leveling agent and a wetting agent, and the brightening agent is sodium polydithio-dipropyl sulfonate (C 6 H 12 O 6 S 4 Na 2 ) 0.018 g/L, leveling agent is sodium dodecyl sulfate (C) 12 H 25 SO 4 Na) 0.08 g/L, and the wetting agent is polyethylene glycol (HO (CH) 2 CH 2 O）nH）0.05g/L。
Copper-based composite materials are widely concerned with their excellent mechanical and physical properties, including high tensile strength and good heat and electrical conductivity, and rapid printing by selective laser sintering technology to obtain high-strength, high-conductivity porous graphite frameworks are considered to be excellent reinforcement material structures in metal-based composite materials. In metal coating treatment, common coating methods are: spraying, electroplating, and the like. The spraying method is simpler, a layer of metal coating is directly sprayed on the surface of the pretreated graphite skeleton by using a spray gun, but the combination of the coating obtained by the method and the graphite skeleton is not firm. The electroplating method is simple and convenient to operate, and the plating layer is well combined, so that the method becomes the best choice for carrying out metallization treatment on the graphite surface. The strength and the electric conduction and heat conduction properties of the embedded framework can be greatly improved by carrying out surface copper plating on the graphite framework preform, so that the graphite framework preform has excellent comprehensive properties and meets the requirements of industrial production.
(8) And (3) preparing the chopped carbon fiber reinforced epoxy resin slurry. Preferably, the chopped carbon fiber with the mass fraction of 0.2-0.5% is fully mixed with the liquid epoxy resin with the mass fraction of 99.5-99.8%, and the epoxy resin slurry reinforced by the chopped carbon fiber is obtained after the bubbles are removed in vacuum.
Carbon fiber is "soft outside and rigid inside", and the quality is lighter than metallic aluminium, but intensity is higher than steel, has corrosion-resistant, high modulus's characteristic. The addition of the chopped carbon fibers can have a relatively obvious effect on improving the mechanical properties of the composite material, the excellent mechanical properties depend on the dispersion condition of the chopped carbon fibers in the resin, the dispersion of the chopped carbon fibers is hindered by the shearing action of stirring and mixing, the dispersion is hindered by the agglomeration, the agglomeration is gradually enhanced along with the increase of the content of the chopped carbon fibers, and the effective contact area of the chopped carbon fibers and the resin is reduced, so that the resin matrix cannot be effectively enhanced, and the mechanical properties of the composite material are reduced. Therefore, when the content of the chopped carbon fibers is increased to a certain extent, the mechanical properties of the composite material are optimal, and when the content of the chopped carbon fibers is below the critical value, the mechanical properties of the composite material are improved along with the increase of the content of the chopped carbon fibers, and when the content of the chopped carbon fibers is above the critical value, the mechanical properties of the composite material are reduced along with the increase of the content of the chopped carbon fibers. According to the research, when the content of the chopped carbon fibers is 0.2-0.5%, the tensile strength and the bending strength of the composite material reach the maximum value.
(9) And (5) compounding. Placing the porous graphite skeleton prepared in the step (7) into a polytetrafluoroethylene mould, pouring the chopped carbon fiber reinforced epoxy resin slurry into the mould through a slip casting process, preserving heat for 1-2h at 80 ℃, then continuously heating up, solidifying the epoxy resin slurry according to the sequence of preserving heat for 1-2h at 120 ℃, preserving heat for 1-2h at 140 ℃ and preserving heat for 1-3h at 160 ℃, cooling to room temperature and demoulding the epoxy resin slurry after solidification is completed, thus obtaining the novel graphite/epoxy resin composite material.
The invention provides a novel graphite/epoxy resin composite material, which has the following advantages:
(1) The mechanical property is good. The graphite is compounded with the epoxy resin matrix in a three-dimensional porous skeleton form to form the interpenetrating network structure composite material, so that the excellent performances of the graphite and the epoxy resin matrix are brought into play, the porous graphite skeleton has better mechanical properties compared with graphite powder, and meanwhile, the epoxy resin matrix is reinforced by the chopped carbon fibers, so that the good mechanical properties of the composite material are ensured.
(2) The conductivity is good. After vacuum pressure impregnation densification, graphitization treatment and overall copper plating, the conductivity of the porous graphite skeleton is improved, so that the conductivity of the composite material is ensured; the porous graphite skeleton has the advantages that all parts connected with each other form a plurality of heat conduction paths, so that the heat conduction performance of the composite material is ensured.
The invention provides a preparation method of a novel graphite/epoxy resin composite material, which has the following advantages:
(1) The preparation method of the novel graphite/epoxy resin composite material has the advantages of environmental protection, rapidness, high efficiency and low cost, and through controllable distribution of the three-dimensional porous graphite skeleton, the electric conduction and heat conduction properties of the graphite composite material are guaranteed, the graphite usage amount is reduced, and the graphite utilization rate is improved.
(2) The three-dimensional porous graphite skeleton structure, the characteristic size and the degree of densification can be actively controlled in the preparation process of the novel graphite/epoxy resin composite material, namely, the number of the electric conduction and heat conduction networks in the composite material can be regulated and controlled according to the industrial application requirements.
Drawings
The invention is further described below with reference to the accompanying drawings:
FIG. 1 is a composite view of a three-dimensional porous copper-plated graphite skeleton and a chopped carbon fiber reinforced epoxy resin, A is a copper-plated porous graphite skeleton, and B is a chopped carbon fiber reinforced epoxy resin matrix.
FIG. 2 is a honeycomb-like graphite skeleton in accordance with an embodiment of the present invention.
FIG. 3 is a diagram of a wood pile porous graphite skeleton in accordance with an embodiment of the present invention.
Fig. 4 is a basic process flow for preparing a novel graphite/epoxy composite material in accordance with an embodiment of the present invention.
Detailed Description
The technical scheme of the invention is explained in detail below with reference to the specific embodiments so as to enable the technical scheme of the invention
Can be more easily understood by a person skilled in the art, so as to more clearly define the scope of protection of the present invention.
Example 1
(1) The natural crystalline flake graphite powder (200 meshes) and the thermosetting phenolic resin powder (500 meshes) are uniformly mixed according to the mass fraction of 7:3, and are put into a dry ball mill for mixing for 4 hours.
(2) The uniformly mixed natural crystalline flake graphite/phenolic resin powder obtained in the step (1) is sintered and molded by selective laser, the laser power is adopted to 17W, and the filling rate is 190 mm x s -1 The three-dimensional porous graphite skeleton biscuit with high heat conduction, continuity, multiple channels and high passageway is prepared by filling the space of 0.1mm, layering thickness of 0.1mm, preheating temperature of 40 ℃ and rapid printing in a contour scanning mode, and the skeleton structure is shown in figure 1.
(3) And (3) placing the graphite skeleton biscuit prepared in the step (2) into a hot air drying oven, preserving heat for 10 minutes at 80 ℃, preserving heat for 20 minutes at 120 ℃ and preserving heat for 10 minutes at 160 ℃ and performing secondary curing treatment to obtain the graphite skeleton preform.
(4) Placing the graphite skeleton preform into a carbonization furnace, vacuumizing to below 100Pa, and heating to 350 ℃ according to a heating rate of 120 ℃/h; at this time, argon with the purity of 99% is introduced, and then the temperature is increased to 600 ℃ at the heating rate of 60 ℃/h; finally, the temperature is increased to 800 ℃ at the heating rate of 240 ℃/h, the heat is preserved for 60 minutes, the furnace is cooled to the room temperature, and the product is taken out. Then under the action of 0.5MPa pressure, impregnating the phenolic resin solution with the concentration of 40% into the carbonized graphite skeleton preform, then drying the carbonized graphite skeleton preform in a hot air drying oven with the temperature of 90 ℃, and repeating the above process for 2 times. Finally, the vacuum degree of the carbonization furnace is increased to below 100Pa, the temperature is increased from room temperature to 100 ℃ at a heating speed of 60 ℃/h, argon or nitrogen with the purity of 99% is introduced, the temperature is increased to 600 ℃ at 240 ℃/h, and finally the temperature is increased to 1500 ℃ at 480 ℃/h, and the temperature is kept for 4 hours; and cooling to room temperature along with the furnace, and taking out to obtain the graphite skeleton preform.
(5) And (3) putting the graphite skeleton preform into a 20g/L sodium hydroxide solution, performing ultrasonic vibration for 8min, removing surface dust and greasy dirt, taking out, and cleaning with deionized water to be neutral. Put into 1000ml of electroplating solution, the proportion is: 98.3 percent of sulfuric acid 30 mL, copper sulfate 100g, acetic acid 2.5 mL and sulfate acid copper plating additive 10mL, wherein the sulfate acid copper plating additive is sodium polydithio-dipropyl sulfonate (C 6 H 12 O 6 S 4 Na 2 ) 0.018 g/L, sodium dodecyl sulfate (C) 12 H 25 SO 4 Na) 0.08 g/L and polyethylene glycol (HO (CH) 2 CH 2 O) nH) 0.05g/L, and the balance of distilled water to prepare 1L of electroplating solution. Electroplating with constant current mode for 30min and current density of 5×10 with graphite skeleton pre-body as cathode and phosphor copper plate as anode 2 A·m -2 . Taking out the plated part, washing with deionized water to neutrality, placing in mixed solution of benzotriazole with mass fraction of 1% and ethanol with mass fraction of 99%, passivating for 15min, taking out, washing with deionized water to neutralAnd (3) drying in a 50 ℃ oven to obtain the copper-plated graphite framework.
(6) Mixing the epoxy resin with excellent fluidity with the chopped carbon fiber according to the mass fraction of 99.8% and 0.2%, and transferring the blend into a vacuum drying oven to remove bubbles after uniform mixing, thus obtaining the chopped carbon fiber reinforced epoxy resin.
(7) Placing the graphite skeleton preform prepared in the step (5) into a polytetrafluoroethylene mold preheated to 40 ℃, pouring the chopped carbon fiber reinforced epoxy resin prepared in the step (6) into the mold through a slip casting process, curing for 2 hours at 80 ℃, then heating to 120 ℃, curing according to the sequence of heat preservation at 120 ℃ for 2 hours and heat preservation at 140 ℃ for 2 hours and heat preservation at 160 ℃ for 3 hours, cooling to room temperature after curing, and demolding to obtain the novel graphite/epoxy resin composite material, wherein the three-dimensional porous copper-plated graphite skeleton and the chopped carbon fiber reinforced epoxy resin are shown in a composite diagram shown in figure 1.
(8) The composite material has the density of 1.88g/cm, the heat conductivity of 48w/m.K, the insulation resistance of 140MΩ under normal state, the wet insulation resistance after alternating damp heat test of 9MΩ, the bending strength of 210Mpa, and the tensile strength of 120Mpa.
The embodiment of the invention can design the framework structure into various structures as shown in figures 2 and 3, and form a three-dimensional porous copper-plated graphite framework and chopped carbon fiber reinforced epoxy resin composite structure diagram together with the chopped carbon fiber reinforced epoxy resin.
Example 2
(1) The natural crystalline flake graphite powder (400 meshes) and the thermosetting phenolic resin powder (600 meshes) are uniformly mixed according to the mass fraction of 8:2, and are put into a dry ball mill for mixing for 5 hours.
(2) And (3) carrying out selective laser sintering molding technology on the uniformly mixed natural crystalline flake graphite/phenolic resin powder obtained in the step (1), adopting a laser power of 15W, a filling rate of 190 mm x s-1, a filling interval of 0.2mm and a layering thickness of 0.2mm, carrying out molding and rapid printing in a contour scanning mode at a preheating temperature of 50 ℃, and obtaining the three-dimensional porous graphite skeleton biscuit with high heat conductivity, continuity, multiple channels, and a skeleton structure shown in figure 2.
(3) And (3) placing the graphite skeleton biscuit prepared in the step (2) into a hot air drying oven, preserving heat for 10 minutes at 80 ℃, preserving heat for 20 minutes at 120 ℃ and preserving heat for 10 minutes at 160 ℃ and performing secondary curing treatment to obtain the graphite skeleton preform.
(4) Placing the graphite skeleton preform into a carbonization furnace, vacuumizing to below 100Pa, and heating to 350 ℃ according to a heating rate of 150 ℃/h; at this time, argon with the purity of 99% is introduced, and then the temperature is increased to 600 ℃ at the heating rate of 70 ℃/h; and finally, heating to 800 ℃ at a heating rate of 200 ℃/h, preserving heat for 60 minutes, cooling to room temperature along with a furnace, and taking out. Then under the action of 0.5MPa pressure, impregnating the phenolic resin solution with the concentration of 40% into the carbonized graphite skeleton preform, then drying the carbonized graphite skeleton preform in a hot air drying oven with the temperature of 80 ℃, and repeating the above process for 3 times. Finally, the vacuum degree of the carbonization furnace is increased to below 100Pa, the temperature is increased from room temperature to 100 ℃ at a heating speed of 60 ℃/h, argon or nitrogen with the purity of 99% is introduced, the temperature is increased to 600 ℃ at 240 ℃/h, and finally the temperature is increased to 1500 ℃ at 480 ℃/h, and the temperature is kept for 4 hours; and cooling to room temperature along with the furnace, and taking out to obtain the graphite skeleton preform.
(5) And (3) putting the graphite skeleton preform into a 20g/L sodium hydroxide solution, performing ultrasonic vibration for 10 min, removing surface dust and greasy dirt, taking out, and cleaning with deionized water to be neutral. Put into 1000ml of electroplating solution, the proportion is: 98.3 percent of sulfuric acid 30 mL, copper sulfate 100g, acetic acid 2.5 mL and sulfate acid copper plating additive 10mL, wherein the sulfate acid copper plating additive is sodium polydithio-dipropyl sulfonate (C 6 H 12 O 6 S 4 Na 2 ) 0.018 g/L, sodium dodecyl sulfate (C) 12 H 25 SO 4 Na) 0.08 g/L and polyethylene glycol (HO (CH) 2 CH 2 O) nH) 0.05g/L, and the balance of distilled water to prepare 1L of electroplating solution. Electroplating with constant current mode for 30min and current density of 5×10 with graphite skeleton pre-body as cathode and phosphor copper plate as anode 2 A·m -2 . Taking out the plated part, washing with deionized water to neutrality, and collecting the plated partPutting the copper-plated graphite skeleton into a mixed solution of benzotriazole with the mass fraction of 1% and ethanol with the mass fraction of 99%, passivating for 15min, taking out, washing with deionized water to be neutral, and drying in a 50 ℃ oven to obtain the copper-plated graphite skeleton.
(6) Mixing the epoxy resin with excellent fluidity with the chopped carbon fiber according to the mass fraction of 99.8% and 0.2%, and transferring the blend into a vacuum drying oven to remove bubbles after uniform mixing, thus obtaining the chopped carbon fiber reinforced epoxy resin.
(7) Placing the graphite skeleton preform prepared in the step (5) into a polytetrafluoroethylene mold preheated to 40 ℃, pouring the chopped carbon fiber reinforced epoxy resin prepared in the step (6) into the mold through a slip casting process, curing for 2 hours at 80 ℃, then heating to 120 ℃, curing according to the sequence of heat preservation at 120 ℃ for 2 hours and heat preservation at 140 ℃ for 2 hours and heat preservation at 160 ℃ for 3 hours, cooling to room temperature after curing, and demolding to obtain the novel graphite/epoxy resin composite material.
(8) The composite material has the density of 1.9g/cm, the heat conductivity of 48w/m.K, the insulation resistance of 150MΩ under normal state, the wet insulation resistance after alternating damp heat test of 8MΩ, the bending strength of 200Mpa, and the tensile strength of 110Mpa.
Example 3
(1) The natural crystalline flake graphite powder (800 meshes) and the thermosetting phenolic resin powder (800 meshes) are uniformly mixed according to the mass fraction of 8:2, and are put into a dry ball mill for mixing for 4 hours.
(2) The uniformly mixed natural crystalline flake graphite/phenolic resin powder obtained in the step (1) is sintered and molded by selective laser, the laser power is 16W, and the filling rate is 190 mm x s -1 The three-dimensional porous graphite skeleton biscuit with high heat conduction, continuity, multiple channels and high passageway is prepared by filling the space of 0.1mm, layering thickness of 0.2mm, preheating temperature of 60 ℃ and rapid printing in a contour scanning mode, and the skeleton structure is shown in figure 3.
(3) And (3) placing the graphite skeleton biscuit prepared in the step (2) into a hot air drying oven, preserving heat for 15 minutes at 80 ℃, preserving heat for 20 minutes at 120 ℃ and preserving heat for 10 minutes at 160 ℃ and performing secondary curing treatment to obtain a graphite skeleton preform.
(4) Placing the graphite skeleton preform into a carbonization furnace, vacuumizing to below 100Pa, and heating to 350 ℃ according to a heating rate of 130 ℃/h; at this time, argon with the purity of 99% is introduced, and then the temperature is increased to 600 ℃ at the heating rate of 80 ℃/h; finally, the temperature is increased to 800 ℃ at the heating rate of 220 ℃/h, the heat is preserved for 60 minutes, the furnace is cooled to the room temperature, and the product is taken out. Then under the action of 0.5MPa pressure, impregnating the phenolic resin solution with the concentration of 40% into the carbonized graphite skeleton preform, then drying the carbonized graphite skeleton preform in a hot air drying oven with the temperature of 80 ℃, and repeating the above process for 2 times. Finally, the vacuum degree of the carbonization furnace is increased to below 100Pa, the temperature is increased from room temperature to 100 ℃ at a heating speed of 60 ℃/h, argon or nitrogen with the purity of 99% is introduced, the temperature is increased to 600 ℃ at 240 ℃/h, and finally the temperature is increased to 1500 ℃ at 480 ℃/h, and the temperature is kept for 4 hours; and cooling to room temperature along with the furnace, and taking out to obtain the graphite skeleton preform.
(5) And (3) putting the graphite skeleton preform into a 20g/L sodium hydroxide solution, performing ultrasonic vibration for 5min, removing surface dust and greasy dirt, taking out, and cleaning with deionized water to be neutral. Put into 1000ml of electroplating solution, the proportion is: 98.3 percent of sulfuric acid 30 mL, copper sulfate 100g, acetic acid 2.5 mL and sulfate acid copper plating additive 10mL, wherein the sulfate acid copper plating additive is sodium polydithio-dipropyl sulfonate (C 6 H 12 O 6 S 4 Na 2 ) 0.018 g/L, sodium dodecyl sulfate (C) 12 H 25 SO 4 Na) 0.08 g/L and polyethylene glycol (HO (CH) 2 CH 2 O) nH) 0.05g/L, and the balance of distilled water to prepare 1L of electroplating solution. Electroplating with constant current mode for 30min and current density of 5×10 with graphite skeleton pre-body as cathode and phosphor copper plate as anode 2 A·m -2 . And taking out the plated part, washing the plated part with deionized water to be neutral, putting the plated part into a mixed solution of benzotriazole with the mass fraction of 1% and ethanol with the mass fraction of 99%, passivating for 15min, taking out the plated part, washing the plated part with deionized water to be neutral, and drying the plated part in a drying oven at 50 ℃ to obtain the copper-plated graphite framework.
(6) Mixing the epoxy resin with excellent fluidity with the chopped carbon fiber according to the mass fraction of 99.8% and 0.2%, and transferring the blend into a vacuum drying oven to remove bubbles after uniform mixing, thus obtaining the chopped carbon fiber reinforced epoxy resin.
(7) Placing the graphite skeleton preform prepared in the step (5) into a polytetrafluoroethylene mold preheated to 40 ℃, pouring the chopped carbon fiber reinforced epoxy resin prepared in the step (6) into the mold through a slip casting process, curing for 2 hours at 80 ℃, then heating to 120 ℃, curing according to the sequence of heat preservation at 120 ℃ for 2 hours and heat preservation at 140 ℃ for 2 hours and heat preservation at 160 ℃ for 3 hours, cooling to room temperature after curing, and demolding to obtain the novel graphite/epoxy resin composite material.
(8) The composite material has the density of 1.88g/cm, the heat conductivity of 47w/m.K, the insulation resistance of 148MΩ under normal state, the wet insulation resistance after alternating damp heat test of 9MΩ, the bending strength of 220Mpa, and the tensile strength of 115Mpa.
Example 4
Substantially the same as in example 1, except that the current density at the time of constant current mode plating in step (5) was 2.5X10. Mu.A.m -2 。
The composite material has the density of 1.85g/cm, the thermal conductivity of 30w/m.K, the insulation resistance of 130MΩ under normal state, the wet insulation resistance after alternating damp heat test of 9MΩ, the bending strength of 210Mpa and the tensile strength of 110Mpa.
Example 5
Substantially the same as in example 1, except that the current density at the time of constant current mode plating in step (5) was 4.0X10. Mu.A.m -2 。
The composite material has the density of 1.88g/cm, the heat conductivity of 40w/m.K, the insulation resistance under normal state of 136MΩ, the wet insulation resistance after alternating damp-heat test of 8.8MΩ, the bending strength of 212Mpa and the tensile strength of 112Mpa.
Example 6
Substantially the same as in example 1, except that the current density at the time of constant current mode plating in step (5) was 5.5X10 a.m -2 。
The composite material has the density of 1.88g/cm, the thermal conductivity of 46w/m.K, the insulation resistance under normal state of 138MΩ, the wet insulation resistance after alternating damp-heat test of 9MΩ, the bending strength of 212Mpa and the tensile strength of 118Mpa.
Example 7
Substantially the same as in example 1, except that the current density at the time of constant current mode plating in step (5) was 6.5X10 a.m -2 。
The composite material has the density of 1.90g/cm, the thermal conductivity of 38w/m.K, the insulation resistance of 135MΩ under normal state, the wet insulation resistance after alternating damp-heat test of 8.9MΩ, the bending strength of 214Mpa and the tensile strength of 110Mpa.
Example 8
Substantially the same as in example 1, except that the plating time in the constant current mode plating in step (5) was 45mins.
The composite material has the density of 1.90g/cm, the heat conductivity of 41w/m.K, the insulation resistance under normal state of 138MΩ, the wet insulation resistance after alternating damp-heat test of 8.9MΩ, the bending strength of 220Mpa and the tensile strength of 112Mpa.
Example 9
Substantially the same as in example 1, except that the plating time in the constant current mode plating in step (5) was 60mins.
The composite material has the density of 1.90g/cm, the heat conductivity of 40w/m.K, the insulation resistance under normal state of 136MΩ, the wet insulation resistance after alternating damp-heat test of 8.85MΩ, the bending strength of 218Mpa and the tensile strength of 110Mpa.
Example 10
Substantially the same as in example 1, except that the epoxy resin excellent in fluidity and the graphite powder in the step (6) were mixed in a ratio of 99.5% by mass to 0.5% by mass.
The composite material has the density of 1.88g/cm, the heat conductivity of 47w/m.K, the insulation resistance of 130MΩ under normal state, the wet insulation resistance after alternating damp heat test of 7.8MΩ, the bending strength of 198Mpa and the tensile strength of 115Mpa.
Example 11
Substantially the same as in example 1, except that the epoxy resin excellent in fluidity and the graphite powder were mixed in a ratio of 99.7% to 0.3% by mass in the step (6).
The composite material has the density of 1.88g/cm, the thermal conductivity of 45w/m.K, the insulation resistance under normal state of 135MΩ, the wet insulation resistance after alternating damp-heat test of 8.3MΩ, the bending strength of 206Mpa and the tensile strength of 119Mpa.
Example 12
Substantially the same as in example 1, except that the copper plating solution in step (5) was formulated as follows: 20ml of sulfuric acid with the mass concentration of more than 98%, 80g of copper sulfate, 2ml of acetic acid and 5ml of sulfate acid copper plating additive.
The composite material has the density of 1.72g/cm, the thermal conductivity of 35w/m.K, the insulation resistance of 105MΩ under normal state, the wet insulation resistance after alternating damp heat test of 6MΩ, the bending strength of 158Mpa, and the tensile strength of 98Mpa.
Example 13
Substantially the same as in example 1, except that the copper plating solution in step (5) was formulated as follows: 20ml of sulfuric acid with the mass concentration of more than 98%, 100g of copper sulfate, 2ml of acetic acid and 5ml of sulfate acid copper plating additive.
The composite material has the density of 1.78g/cm, the heat conductivity of 39w/m.K, the insulation resistance of 118MΩ under normal state, the wet insulation resistance after alternating damp heat test of 8MΩ, the bending strength of 178Mpa and the tensile strength of 104Mpa.
Example 14
Substantially the same as in example 1, except that the copper plating solution in step (5) was formulated as follows: 40ml of sulfuric acid with the mass concentration of more than 98%, 80g of copper sulfate, 2ml of acetic acid and 5ml of sulfate acid copper plating additive.
The composite material has the density of 1.82g/cm, the heat conductivity of 41w/m.K, the insulation resistance of 122MΩ under normal state, the wet insulation resistance after alternating damp heat test of 8.5MΩ, the bending strength of 188Mpa and the tensile strength of 109Mpa.
Example 15
Substantially the same as in example 1, except that the copper plating solution in step (5) was formulated as follows: 40ml of sulfuric acid with the mass concentration of more than 98%, 120g of copper sulfate, 5ml of acetic acid and 15ml of sulfate acid copper plating additive.
The composite material has the density of 1.83g/cm, the thermal conductivity of 44w/m.K, the insulation resistance under normal state of 129MΩ, the wet insulation resistance after alternating damp-heat test of 8.6MΩ, the bending strength of 208Mpa and the tensile strength of 110Mpa.
Example 16
Substantially the same as in example 1, except that the copper plating solution in step (5) was formulated as follows: 40ml of sulfuric acid with the mass concentration of more than 98%, 120g of copper sulfate, 2ml of acetic acid and 5ml of sulfate acid copper plating additive.
The composite material has the density of 1.82g/cm, the heat conductivity of 40w/m.K, the insulation resistance of 130MΩ under normal state, the wet insulation resistance after alternating damp heat test of 8.8MΩ, the bending strength of 207Mpa, and the tensile strength of 110Mpa.
Example 17
Substantially the same as in example 1, except that the copper plating solution in step (5) was formulated as follows: 40ml of sulfuric acid with the mass concentration of more than 98%, 120g of copper sulfate, 4ml of acetic acid and 10ml of sulfate acid copper plating additive.
The composite material has the density of 1.87g/cm, the thermal conductivity of 46w/m.K, the insulation resistance under normal state of 133MΩ, the wet insulation resistance after alternating damp-heat test of 8.5MΩ, the bending strength of 200Mpa, and the tensile strength of 112Mpa.
Example 18
Substantially the same as in example 1, except that the copper plating solution in step (5) was formulated as follows: 20ml of sulfuric acid with the mass concentration of more than 98%, 120g of copper sulfate, 5ml of acetic acid and 15ml of sulfate acid copper plating additive.
The composite material has the density of 1.79g/cm, the heat conductivity of 40w/m.K, the insulation resistance under normal state of 130MΩ, the wet insulation resistance after alternating damp-heat test of 8.7MΩ, the bending strength of 205Mpa and the tensile strength of 114Mpa.
The prepared novel graphite/epoxy resin has the advantages of not being most excellent in heat conductivity, strength, insulation resistance and the like, but better in comprehensive performance than metal materials and organic materials, has no obvious defects, is easier in performance regulation and control, and has wide application prospects in the fields of communication engineering and electronic instrument and meter industries.
Claims (9)
1. The preparation method of the graphite/epoxy resin composite material is characterized by comprising the following steps:
(1) Preparing natural crystalline flake graphite/thermosetting phenolic resin mixed powder;
(2) Rapidly printing a porous graphite skeleton prototype by using a selective laser sintering molding technology to finish secondary solidification to obtain a porous graphite skeleton biscuit;
(3) Carbonizing the porous graphite skeleton biscuit;
(4) Impregnating phenolic resin liquid under vacuum pressure to carry out densification treatment;
(5) Repeating the steps (3) and (4) for 2-3 times to obtain a high-density porous graphite skeleton preform;
(6) Graphitizing to obtain a porous graphite skeleton preform with high electric conductivity and high heat conductivity;
(7) Copper plating is carried out on the surface of the porous graphite skeleton preform to obtain the three-dimensional porous copper-plated graphiteThe technological parameters of the skeleton and the surface copper plating are as follows: cleaning the prepared graphite skeleton preform, placing into electroplating solution, electroplating with constant current mode with graphite preform as cathode and phosphor copper plate as anode for 30-60min and current density of 2×10-7×10 A.m -2 Taking out a plated part, washing the plated part with water to be neutral, placing the plated part in a mixed solution of benzotriazole with the mass fraction of 1-5% and ethanol with the mass fraction of 95-99%, passivating for 15-30min, washing the plated part with water to be neutral, and drying to obtain a copper-plated porous graphite skeleton preform, wherein the ratio of the electroplating solution is as follows: 20-40ml of sulfuric acid with the mass concentration of more than 98%, 80-120g of copper sulfate, 2-5ml of acetic acid, 5-15ml of sulfate acid copper plating additive and water are added to prepare 1L of electroplating solution;
(8) Preparing chopped carbon fiber reinforced epoxy resin slurry, fully mixing 0.2-0.5% of chopped carbon fiber by mass fraction with 99.5-99.8% of liquid epoxy resin by mass fraction, and removing bubbles in vacuum to obtain the chopped carbon fiber reinforced epoxy resin slurry;
(9) Placing the three-dimensional porous copper-plated graphite skeleton prepared in the step (7) in a mould, fully penetrating the chopped carbon fiber reinforced epoxy resin slurry into the porous graphite skeleton through a slip casting process, and then solidifying, cooling and demoulding to obtain the novel graphite/epoxy resin composite material.
2. The method for preparing a graphite/epoxy resin composite material according to claim 1, wherein the natural flake graphite powder in the step (1) is 200-800 mesh, the mass fraction is 60-90%, and the carbon content is not less than 99%; 200-900 meshes of thermosetting phenolic resin powder, and 10-40% of thermosetting phenolic resin powder by mass fraction; adding the mixture into a dry ball mill, and mixing for 4-6 hours to obtain graphite/phenolic resin mixed powder.
3. The method of preparing a graphite/epoxy composite material according to claim 1, wherein the combination of the selective laser sintering process parameters in step (2) is as follows: laser power 12W-17W, filling rate 1300-190 mm s -1 Filling space is 0.1-0.2mm, and layering thickness is 0.1-0.3mmPreheating at 40-60 deg.c, and contour scanning to form.
4. The method of preparing a graphite/epoxy resin composite material according to claim 1, wherein the secondary curing process parameters in the step (2) are as follows: heating to 80-90 deg.c from room temperature, maintaining for 5-15 min, heating to 120-130 deg.c, maintaining for 10-30 min, heating to 160-180 deg.c and maintaining for 10-30 min.
5. The method of preparing a graphite/epoxy resin composite material according to claim 1, wherein the carbonization process parameters in step (3) are combined as follows: firstly, vacuumizing a carbonization furnace to below 100Pa, and introducing argon or nitrogen with the purity of 99% from room temperature to 350 ℃ at the speed of 60 ℃/h to 150 ℃/h; heating to 600 ℃ at a speed of 30-120 ℃/h; finally, heating to 800 ℃ at 180-240 ℃ per hour, preserving heat for 30-60 minutes, and cooling to room temperature along with the furnace.
6. The method of claim 1, wherein in the step (4), the vacuum pressure impregnation process parameters are combined as follows: vacuum pumping is carried out to below 100Pa, then phenolic resin solution with the mass concentration of 20-40% is immersed into the carbonized graphite skeleton preform under the pressure of 0.3-0.5MPa, and then the carbonized graphite skeleton preform is dried in a hot air drying oven with the temperature lower than 100 ℃.
7. The method of preparing a graphite/epoxy resin composite material according to claim 1, wherein in the step (6), the graphitization process parameters are as follows: firstly, pumping the vacuum degree of a carbonization furnace to be lower than 100Pa, heating the carbonization furnace to 350 ℃ from room temperature at a heating speed of 50-60 ℃ per hour, introducing argon or nitrogen with purity higher than 99%, heating the carbonization furnace to 2000-2600 ℃ at a heating speed of 180-360 ℃ per hour, and preserving heat for 1-2 hours; and finally cooling to room temperature along with the furnace, and taking out to obtain the high-heat-conductivity high-strength porous graphite skeleton preform.
8. According to claim 1The preparation method of the graphite/epoxy resin composite material is characterized in that the sulfate acid copper plating additive is a mixed solution composed of a brightening agent, a leveling agent and a wetting agent, and the brightening agent is sodium polydithio-dipropyl sulfonate (C) 6 H 12 O 6 S 4 Na 2 ) 0.018 g/L, leveling agent is sodium dodecyl sulfate (C) 12 H 25 SO 4 Na) 0.08 g/L, and the wetting agent is polyethylene glycol (HO (CH) 2 CH 2 O）nH）0.05g/L。
9. The method for preparing a graphite/epoxy resin composite material according to claim 1, wherein in the step (9), the prepared porous graphite skeleton is placed in a polytetrafluoroethylene mold, the chopped carbon fiber reinforced epoxy resin slurry is poured into the polytetrafluoroethylene mold through a slip casting process, the temperature is kept at 80 ℃ for 1-2 hours, then the temperature is continuously raised, the curing is carried out according to the heat preservation at 120 ℃ for 1-2 hours, the heat preservation at 140 ℃ for 1-2 hours and the heat preservation at 160 ℃ for 1-3 hours, and after the curing is completed, the mold is cooled to room temperature and removed from the mold, so that the novel graphite/epoxy resin composite material is obtained.
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