CN117903639A - Graphene and fluorocarbon resin composite lightweight grounding material and preparation method thereof - Google Patents
Graphene and fluorocarbon resin composite lightweight grounding material and preparation method thereof Download PDFInfo
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- CN117903639A CN117903639A CN202410317525.1A CN202410317525A CN117903639A CN 117903639 A CN117903639 A CN 117903639A CN 202410317525 A CN202410317525 A CN 202410317525A CN 117903639 A CN117903639 A CN 117903639A
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- Prior art keywords
- graphene
- silicon nitride
- parts
- fluorocarbon resin
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 198
- 239000000463 material Substances 0.000 title claims abstract description 104
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000000805 composite resin Substances 0.000 title description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical class N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 129
- 239000011347 resin Substances 0.000 claims abstract description 106
- 229920005989 resin Polymers 0.000 claims abstract description 106
- 229920001046 Nanocellulose Polymers 0.000 claims abstract description 100
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- 238000005260 corrosion Methods 0.000 claims abstract description 83
- 239000000843 powder Substances 0.000 claims abstract description 78
- 239000011159 matrix material Substances 0.000 claims abstract description 52
- 239000002904 solvent Substances 0.000 claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 18
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- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 8
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 8
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- 229920000570 polyether Polymers 0.000 claims description 7
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 6
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 claims description 6
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- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 5
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 4
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 claims description 4
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- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 4
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- 239000012279 sodium borohydride Substances 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 3
- 239000002480 mineral oil Substances 0.000 claims description 3
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- 125000005375 organosiloxane group Chemical group 0.000 claims description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- 229940071870 hydroiodic acid Drugs 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 description 37
- 239000001913 cellulose Substances 0.000 description 37
- 239000002121 nanofiber Substances 0.000 description 31
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 21
- 229910052802 copper Inorganic materials 0.000 description 20
- 239000010949 copper Substances 0.000 description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
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- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
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- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 150000001721 carbon Chemical group 0.000 description 1
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- 239000001257 hydrogen Substances 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
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- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
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- 230000036961 partial effect Effects 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
- H01R4/00—Electrically-conductive connections between two or more conductive members in direct contact, i.e. touching one another; Means for effecting or maintaining such contact; Electrically-conductive connections having two or more spaced connecting locations for conductors and using contact members penetrating insulation
- H01R4/58—Electrically-conductive connections between two or more conductive members in direct contact, i.e. touching one another; Means for effecting or maintaining such contact; Electrically-conductive connections having two or more spaced connecting locations for conductors and using contact members penetrating insulation characterised by the form or material of the contacting members
- H01R4/66—Connections with the terrestrial mass, e.g. earth plate, earth pin
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
- H01R43/00—Apparatus or processes specially adapted for manufacturing, assembling, maintaining, or repairing of line connectors or current collectors or for joining electric conductors
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
- Paints Or Removers (AREA)
Abstract
The invention provides a lightweight grounding material compounded by graphene and fluorocarbon resin and a preparation method thereof, and belongs to the technical field of lightweight grounding materials, wherein the lightweight grounding material comprises a metal matrix and an anti-corrosion conductive coating coated on the surface of the metal matrix; the anticorrosion conductive coating comprises fluorocarbon resin, modified graphene, modified silicon nitride powder, nanocellulose, a defoaming agent, a leveling agent and a solvent. According to the invention, the anti-corrosion conductive coating is formed on the surface of the metal matrix, the anti-corrosion conductive coating takes fluorocarbon resin as a matrix, and modified graphene, modified silicon nitride powder and nanocellulose are added, so that the overall wear resistance, heat conduction and mechanical properties of the grounding material can be greatly improved.
Description
Technical Field
The invention belongs to the technical field of lightweight grounding materials, and relates to a lightweight grounding material compounded by graphene and fluorocarbon resin and a preparation method thereof.
Background
Grounding is an important means for ensuring the safety of equipment, buildings, personal safety, such as electric power, communication, microelectronic equipment, and the like. With advances in power, microelectronics, and point science, there is also an increasing demand for grounding systems. In recent years, equipment damage caused by poor grounding systems frequently occurs, particularly, the grounding device corrodes in thunderstorm seasons, so that the grounding resistance value is increased, the thermal stability of the grounding system is reduced, and the caused equipment damage caused by lightning strike also frequently occurs. With the continuous increase of the capacity of the power system, the requirements for safe operation of the grounding network are more and more strict, and the requirements for the stability of the grounding resistance of the pole tower are also higher.
At present, the grounding body of the power system mainly faces the problems of corrosion, abrasion, resistance reduction and high density, and a great deal of grounding technical research has been carried out at home and abroad for a long time. The invention patent with publication number CN104701644A provides a graphite composite grounding protection material and a preparation method thereof, wherein the graphite composite grounding protection material comprises the following raw materials in percentage by volume: 40-70% of flake graphite, 25-55% of cement, 2-5% of asphalt and 2-5% of epoxy resin. The invention patent with publication number CN107227083A provides a lightning-proof corrosion-proof grounding material and a preparation method thereof, wherein the grounding material comprises a metal matrix material and a conductive protective film layer from inside to outside, and the conductive protective film layer comprises a conversion film layer, a sealing layer and a conductive surface layer from inside to outside; the conversion coating layer comprises the following raw materials in parts by weight: 2-6 parts of zinc sulfate, 3-8 parts of titanium nitrate, 1-5 parts of ammonium molybdate, 3-8 parts of scrap iron and 10-22 parts of deionized water; the conductive surface layer comprises the following raw materials in parts by weight: 10-25 parts of nano conductive carbon, 10-20 parts of modified acrylic resin, 5-12 parts of ferrophosphorus powder, 1-5 parts of silane coupling agent, 30-40 parts of toluene and 40-60 parts of ethyl acetate.
However, the technical solution provided by the above patent only solves the technical problems in a certain aspect, and cannot simultaneously achieve various advantages such as corrosion resistance, wear resistance, renting reduction, light weight and the like. Therefore, there is a need to modify the existing grounding materials to simultaneously achieve various excellent properties required for practical use.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a lightweight grounding material compounded by graphene and fluorocarbon resin and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a lightweight grounding material compounded by graphene and fluorocarbon resin, which comprises a metal matrix and an anti-corrosion conductive coating coated on the surface of the metal matrix;
the anticorrosion conductive coating comprises fluorocarbon resin, modified graphene, modified silicon nitride powder, nanocellulose, a defoaming agent, a leveling agent and a solvent.
According to the invention, the anti-corrosion conductive coating is formed on the surface of the metal matrix, the anti-corrosion conductive coating takes fluorocarbon resin as a matrix, and modified graphene, modified silicon nitride powder and nanocellulose are added, so that the overall wear resistance, heat conduction and mechanical properties of the grounding material can be greatly improved.
The anticorrosive conductive coating takes fluorocarbon resin as a matrix, and modified graphene is added, so that the modified graphene has extremely high heat conductivity and a special two-dimensional lamellar structure, can be used as an enhancement phase and a lubrication phase in the fluorocarbon resin matrix at the same time, and obviously improves the heat conductivity and wear resistance of the anticorrosive conductive coating. On one hand, the modified graphene has excellent heat conduction performance, so that friction heat generated at a friction interface can be timely conducted out in the friction and abrasion process of the grounding material, and the thermal damage to the grounding material due to high temperature is reduced; on the other hand, the modified graphene is a two-dimensional lamellar nano material, so that the modified graphene has an excellent interlayer sliding effect, is an ideal lubricating additive, and can improve the wear resistance of the anti-corrosion conductive coating.
According to the invention, the modified silicon nitride powder is also added into the fluorocarbon resin matrix, and can be dispersed on the surface and between the sheets of the modified graphene, so that the interlayer spacing between the sheets of the modified graphene is increased; meanwhile, the modified graphene also provides nucleation sites for the modified silicon nitride, so that the dispersibility of the modified silicon nitride is further improved. In addition, the modified silicon nitride powder fills up the defects of gaps, holes and the like in the fluorocarbon resin matrix to a certain extent, reduces the stress concentration phenomenon in the fluorocarbon resin matrix, and ensures that the prepared grounding material is not easy to generate brittle fracture.
Cellulose is a natural renewable biomass polymer material, and has the advantages of wide source, high thermal stability, biodegradability and the like. Nanocellulose is a nanoscale cellulose that can be divided into cellulose nanocrystals and cellulose nanofibers. The invention preferably adopts the cellulose nanofiber with the fibrillar structure with high length-diameter ratio, has the advantages of excellent mechanical property, light weight, high strength and the like, and the prepared grounding material can have the characteristics of light weight, high strength by being doped into the light weight grounding material. In addition, the nanocellulose can form a continuous network structure around the modified graphene and the modified silicon nitride powder under the action of natural force, so that the filler can be uniformly dispersed and spread, and therefore, the nanocellulose can be used as a stable dispersing agent for the modified graphene and the modified silicon nitride powder, and the dispersing effect of the modified graphene and the modified silicon nitride powder in a fluorocarbon resin matrix is remarkably improved. Meanwhile, the cellulose nanofiber is used as a long-chain fibrous nanomaterial, fiber filaments can be mutually interwoven to generate physical winding, the cellulose nanofiber can be used as a structural support material in a fluorocarbon resin matrix, and when the cellulose nanofiber is dispersed in a solvent, sol with a three-dimensional network structure can be formed, and the structure can promote the infiltration of fluorocarbon resin emulsion on one hand, so that the effective contact area between the fluorocarbon resin matrix and nanocellulose is improved, and the stress conduction in an anti-corrosion conductive coating is facilitated; on the other hand, a plurality of mutually communicated heat conduction passages exist in the three-dimensional network structure formed by physically crossing and winding the nanocellulose, a three-dimensional filler framework is constructed, modified graphene and modified silicon nitride powder can be attached to the surface of the heat conduction passages, and the structure enables a higher heat conduction coefficient to be achieved by adopting a lower-content filler.
As a preferable technical scheme of the invention, the anti-corrosion conductive coating comprises the following components in parts by weight:
40-60 parts of fluorocarbon resin;
2-5 parts of modified graphene;
1-5 parts of modified silicon nitride powder;
0.5-1.5 parts of nanocellulose;
1-5 parts of a defoaming agent;
1-5 parts of flatting agent;
10-20 parts of solvent.
Wherein, the weight parts of the fluorocarbon resin can be 40 parts, 42 parts, 44 parts, 46 parts, 48 parts, 50 parts, 52 parts, 54 parts, 56 parts, 58 parts or 60 parts; the weight parts of the modified graphene may be 2.0 parts, 2.2 parts, 2.4 parts, 2.6 parts, 2.8 parts, 3.0 parts, 3.2 parts, 3.4 parts, 3.6 parts, 3.8 parts, 4.0 parts, 4.2 parts, 4.4 parts, 4.6 parts, 4.8 parts, or 5.0 parts; the weight parts of the modified silicon nitride powder may be 1.0 part, 1.5 parts, 2.0 parts, 2.5 parts, 3.0 parts, 3.5 parts, 4.0 parts, 4.5 parts, or 5.0 parts; the weight parts of nanocellulose may be 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, or 1.5; the defoamer may be 1.0 part, 1.5 parts, 2.0 parts, 2.5 parts, 3.0 parts, 3.5 parts, 4.0 parts, 4.5 parts, or 5.0 parts by weight; the leveling agent may be 1.0 part, 1.5 parts, 2.0 parts, 2.5 parts, 3.0 parts, 3.5 parts, 4.0 parts, 4.5 parts, or 5.0 parts by weight; the solvent may be 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts or 20 parts by weight, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
According to the invention, the wear resistance, mechanical property and heat conduction property of the whole grounding material are enhanced by adding the modified graphene, the modified silicon nitride powder and the nanocellulose, and whether the properties of the modified graphene, the modified silicon nitride powder and the nanocellulose can influence the comprehensive properties of the anti-corrosion heat conduction coating or not is considered, and the anti-corrosion heat conduction coating is mainly characterized in that the mechanical strength, the bearing capacity, the heat stability, the heat conduction property and the like of the modified graphene, the modified silicon nitride powder and the nanocellulose are realized. Secondly, the addition amount of the modified graphene, the modified silicon nitride powder and the nanocellulose, the dispersibility in a fluorocarbon resin matrix and the combination mode among the modified graphene, the modified silicon nitride powder and the nanocellulose also have very important influence on the overall wear resistance, mechanical property and heat conductivity of the anti-corrosion heat-conducting coating.
When the addition amount of the modified graphene, the modified silicon nitride powder and the nanocellulose is too low, the comprehensive performance of the anti-corrosion heat-conducting coating is reduced, and the improvement on the wear resistance, the mechanical property and the heat conductivity of the anti-corrosion heat-conducting coating is very limited; when the addition amount of the modified graphene, the modified silicon nitride powder and the nanocellulose is too high, the dispersibility of the modified graphene, the modified silicon nitride powder and the nanocellulose in the lightweight grounding material is reduced, the agglomeration phenomenon is easy to occur, so that the interface bonding strength between the modified graphene, the modified silicon nitride powder, the nanocellulose and the fluorocarbon resin matrix is reduced, a large number of stress concentration points are easy to generate in the fluorocarbon resin matrix and on the surface under the action of an external load, microcracks are generated on the surface and in the grounding material, the reinforcing effect of the filler on the fluorocarbon resin matrix cannot be effectively exerted, and meanwhile, the abrasion mode of the fluorocarbon resin matrix can be possibly changed in the friction process, so that a large amount of material loss is generated. In addition, the fillers such as modified graphene and modified silicon nitride powder can be attached to the nanocellulose to generate more contact gaps, and the contact gaps can have adverse effects on the tensile properties of the anti-corrosion heat-conducting coating.
According to the invention, the modified graphene with a two-dimensional layered structure, the nanocellulose with a one-dimensional fibrous structure and the modified silicon nitride powder with a zero-dimensional granular structure are combined to form a multi-layer structure, which is beneficial to forming an effective heat conduction channel in a fluorocarbon resin matrix. When the addition amount of the modified graphene, the modified silicon nitride powder and the nanocellulose is within the weight part range defined by the invention, the modified graphene and the modified silicon nitride powder can be fully contacted with the nanocellulose, so that the modified graphene and the modified silicon nitride powder are effectively distributed on the surface and the inside of a pore canal of a three-dimensional network structure formed by the nanocellulose, and a three-dimensional heat conduction network structure is formed; meanwhile, interlayer gaps of the modified graphene are filled with the modified nano silicon powder, so that the influence of interface thermal resistance is relieved. The three-dimensional structure reduces the conduction discontinuity of heat in the thickness direction of the grounding material, and improves the vibration frequency and the transmission efficiency in the length direction of the grounding material, so that the heat conduction capacity of the grounding material is greatly improved.
The graphene has a stable hexagonal honeycomb lamellar structure, excellent heat conduction capability and remarkable surface effect, and can be added into a lightweight grounding material to endow the grounding material with the characteristics of excellent physical barrier property, chemical stability resistance, oxidation resistance, corrosion resistance and the like. In addition, the modified graphene with the two-dimensional lamellar structure generates a labyrinth effect in the grounding material, so that the penetration path of corrosive media in the grounding material is increased, and the corrosion resistance of the grounding material is enhanced.
The mechanism of the modified graphene playing the anti-corrosion and anti-corrosion role in the anti-corrosion heat-conducting coating comprises: (1) After the modified graphene is added, the corrosion-resistant heat-conducting coating can exert a good physical barrier effect on the metal matrix, the graphene is formed by sp2 hybridization of carbon atoms, the stable two-dimensional lamellar structure of the graphene can block the metal matrix from a corrosion medium, the corrosion medium is prevented from penetrating into the metal matrix, and the corrosion resistance of the corrosion-resistant heat-conducting coating is effectively enhanced; (2) The graphene is a carbon nanomaterial, has a small size, can be filled into pores and holes in the anti-corrosion heat-conducting coating after being uniformly mixed with other coating components, has good hydrophobicity, and can well prevent water molecules from penetrating from the surface of the anti-corrosion heat-conducting coating, so that an anti-corrosion effect is achieved; (3) The graphene has super-strong electric conductivity, and can timely transfer and conduct away charged particles generated by electrochemical reaction on the surface of the metal substrate, so that the metal substrate is passivated, and the protective capability of the anti-corrosion heat-conducting coating is enhanced.
The addition amount of the modified graphene has a great influence on the stability of the anti-corrosion heat-conducting paint, and the invention particularly limits the addition amount of the modified graphene to 2-5 parts by weight. When the addition amount of the modified graphene exceeds 5 parts by weight, the stability of the anti-corrosion heat-conducting coating gradually decreases. The viscosity of the anticorrosive heat-conducting paint is increased along with the increase of the addition amount of the modified graphene, so that the flowability and the stability of the anticorrosive heat-conducting paint are directly influenced; on the other hand, as the addition amount of the modified graphene is increased, the lamellar spacing of the modified graphene is reduced, the specific surface area of the modified graphene is higher, the acting force between the lamellar of the modified graphene is increased due to the corresponding high surface energy, the agglomeration phenomenon is extremely easy to generate, the modified graphene is separated from fluorocarbon resin emulsion, the stability of the anti-corrosion heat-conducting coating is indirectly reduced, defects such as gaps and holes on the surface and the end face of the anti-corrosion heat-conducting coating formed after film formation are increased, and the surface is not compact any more.
The invention particularly limits the adding amount of the modified silicon nitride powder to 1-5 parts by weight, when the adding amount of the modified silicon nitride powder exceeds 5 parts by weight, the modified silicon nitride powder can cause agglomeration phenomenon in fluorocarbon resin to form granular substances, and the granular substances have poor dispersibility in the fluorocarbon resin, because the modified silicon nitride powder has smaller particle size and larger specific surface area and larger surface energy, the mutual attraction between the modified silicon nitride powder particles is caused to agglomerate, so that a uniform and compact anti-corrosion heat-conducting coating cannot be formed, on one hand, stress concentration phenomenon can be generated, and on the other hand, good anti-corrosion protection effect on a metal matrix cannot be achieved.
The molecular structure of the nanocellulose has a large number of hydrophilic functional groups-OH and-COOH, so that the nanocellulose has excellent dispersing effect in water and can be stably dispersed. Because the nanocellulose contains a large amount of-COOH, electrostatic repulsion can be generated between different nanocellulose, and steric hindrance exists between the one-dimensional nanocellulose and the two-dimensional modified graphene, so that obvious aggregation phenomenon of the modified graphene in the nanocellulose solution can not occur due to the dual effects of electrostatic repulsion and steric hindrance, stable dispersed dispersion solution can be obtained, and the uniformity of the anti-corrosion heat-conducting coating can be improved.
The invention particularly limits the addition amount of the nano cellulose to 0.5-1.5 parts, when the addition amount of the nano cellulose is lower than 0.5 parts by weight, the nano cellulose cannot form a complete three-dimensional network structure, the number of heat conduction paths formed by physically winding the nano cellulose in the anti-corrosion heat conduction coating is limited, and certain contact thermal resistance exists between the structures, so that the heat conduction paths cannot be completely communicated; meanwhile, due to the fact that the addition amount of the nanocellulose is too small, good crosslinking and compounding can not be formed between the modified silicon nitride powder and the modified graphene and the nanocellulose, and further the improvement effect on the mechanical property and the heat conducting property of the anti-corrosion heat conducting coating is not obvious. With the improvement of the addition amount of the nanocellulose, the modified silicon nitride powder, the modified graphene and the nanocellulose are fully contacted, a large number of three-dimensional network crosslinking structures are constructed, the influence of interface thermal resistance is reduced, and the improvement of the heat conduction capacity of the anti-corrosion heat conduction coating is facilitated; meanwhile, the synergistic effect among the modified silicon nitride powder, the modified graphene and the nanocellulose is enhanced, and the impact strength of the anti-corrosion heat-conducting coating is greatly improved. However, when the addition amount of the nanocellulose exceeds 1.5 parts by weight, the viscosity of the anti-corrosion heat-conducting coating is too high, the fluidity is poor, the nanocellulose is agglomerated, the interfacial thermal resistance is increased to a certain extent, and the synergistic effect among the modified silicon nitride powder, the modified graphene and the nanocellulose is inhibited to a certain extent; meanwhile, the interfacial compatibility between the nanocellulose and the fluorocarbon resin matrix is poor, so that defects such as holes and gaps appear in the anti-corrosion heat-conducting coating, and in the stretching process, stress concentration appears in the anti-corrosion heat-conducting coating due to the defects, so that the impact strength of the anti-corrosion heat-conducting coating is reduced.
As a preferable technical scheme of the invention, the defoaming agent is any one or a combination of at least two of an organosiloxane defoaming agent, a mineral oil defoaming agent and a polyether defoaming agent.
In some preferred examples, the leveling agent is any one or a combination of at least two of diacetone alcohol, isophorone, acrylate, polyether siloxane, polydimethylsiloxane.
In some preferred examples, the solvent is any one or a combination of at least two of deionized water, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, and tert-butanol.
In a second aspect, the present invention provides a method for preparing the lightweight grounding material according to the first aspect, the method comprising:
Mixing fluorocarbon resin, a defoaming agent and a leveling agent in proportion, and uniformly stirring to obtain resin emulsion;
(II) mixing nanocellulose with a solvent in proportion to obtain a nanocellulose solution, dispersing modified graphene and modified silicon nitride powder in the nanocellulose solution, and uniformly stirring to obtain a dispersion solution;
and (III) mixing the resin emulsion obtained in the step (I) with the dispersion solution obtained in the step (II), uniformly stirring to obtain the anti-corrosion conductive coating, coating the anti-corrosion conductive coating on the surface of the metal matrix, and drying to obtain the lightweight grounding material.
The nano cellulose has various forms in nature, has the characteristics of high strength, high modulus, high flexibility, reproducibility and the like, has a large number of hydroxyl groups and carboxyl groups on the surface, is easy to carry out various surface modifications so as to change the polarity, and can be better combined with a fluorocarbon resin matrix after changing the polarity so as to improve the mechanical property of the anti-corrosion heat-conducting coating.
The invention preferably adopts the heat soaking treatment of sodium hydroxide solution to the nano cellulose, and then the carboxylation modification treatment is carried out to the nano cellulose through a TEMPO oxidation system. The interface compatibility between the nanocellulose and the fluorocarbon resin matrix is greatly improved through the modification treatment mode, slip between the nanocellulose and the fluorocarbon resin matrix is avoided in the stress process, pores inside the anti-corrosion heat-conducting coating are filled to a certain extent, and stress concentration is reduced.
After the nano cellulose is subjected to heat soaking treatment by sodium hydroxide solution, a swelling effect can be generated on the nano cellulose, the effective contact area between the swelled nano cellulose and the fluorocarbon resin matrix can be increased, and the interface strength between the swelled nano cellulose and the fluorocarbon resin matrix can be improved by the increase of the effective contact area. In addition, after the heat soaking treatment by the sodium hydroxide solution, the crystallinity of the nano cellulose is optimized, the molecular chain of the nano cellulose is promoted to be readjusted, the molecular structure is optimized, and the nano cellulose becomes relatively regular, so that the mechanical reinforcing effect of the nano cellulose is fully exerted.
In the TEMPO oxidation process, the hydroxyl group at the C6 position in the molecular chain of the nanocellulose is oxidized into a carboxyl group, so that the hydrophilicity of the nanocellulose is improved, and the nanocellulose can be stably dispersed in a solvent. Meanwhile, the dispersion stability of the modified graphene in the nano cellulose solution is improved, and the carboxyl modified nano cellulose and the modified graphene with partial oxygen-containing groups have hydrogen bond action. In addition, since nanocellulose has amphipathy, it can ionize in solvent to obtain negative charge; meanwhile, the modified graphene can be ionized in the nano cellulose solution to obtain negative charge, and the agglomeration phenomenon of the modified graphene in the nano cellulose solution is not easy to occur based on the electrostatic repulsive force effect between the modified graphene and the nano cellulose solution. The good dispersibility is beneficial to uniform mixing of the modified graphene and the nanocellulose. In addition, as the modified silicon nitride is loaded on the surface and in the sheet layer of the modified graphene, the modified silicon nitride loaded on the modified graphene can be uniformly dispersed in the nano cellulose solution along with the uniform dispersion of the modified graphene in the nano cellulose solution, and a precondition is provided for the uniform degree of the subsequent mixing of the dispersion solution and the resin emulsion.
As a preferable technical scheme of the invention, in the step (I), the stirring mode is mechanical stirring.
In some preferred examples, the mechanical stirring speed is 600-800r/min, for example 600r/min, 620r/min, 640r/min, 660r/min, 680r/min, 700r/min, 720r/min, 740r/min, 760r/min, 780r/min or 800r/min, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
In some preferred examples, the mechanical agitation time is 5-10min, for example, 5.0min, 5.5min, 6.0min, 6.5min, 7.0min, 7.5min, 8.0min, 8.5min, 9.0min, 9.5min, or 10.0min, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
As a preferable technical scheme of the invention, in the step (II), the modified graphene is prepared by adopting the following method:
(1) Dispersing graphene oxide in deionized water, and performing ultrasonic dispersion to obtain graphene oxide dispersion liquid;
(2) Adding a hydroxyl modifier into the graphene oxide dispersion liquid, continuously stirring, carrying out hydroxylation modification on graphene oxide to obtain a reaction product, and washing and filtering the reaction product to obtain a filter cake;
(3) Dispersing the filter cake in a solvent to obtain a suspension, adding a reducing agent into the suspension for reflux reaction, and centrifugally filtering, washing and drying the reaction product after the reaction is finished to obtain the modified graphene.
In a preferred embodiment of the present invention, in the step (2), the hydroxyl modifier is any one or a combination of at least two of triethanolamine, polyvinyl alcohol, triisopropanolamine and N-methyldiethanolamine.
In some preferred examples, the mass ratio of graphene oxide to the hydroxyl modifier is 1 (10-20), for example, may be 1:10, 1:11, 1:12, 1:13, 1:14, 1:15, 1:16, 1:17, 1:18, 1:19 or 1:20, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
In some preferred examples, in the step (3), the mass ratio of the graphene oxide to the reducing agent is 1 (1-1.5), for example, may be 1:1, 1:1.05, 1:1.1, 1:1.15, 1:1.2, 1:1.25, 1:1.3, 1:1.35, 1:1.4, 1:1.45 or 1:5, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
In some preferred examples, the reducing agent is any one or a combination of at least two of hydrazine hydrate, sodium borohydride, glucose, ascorbic acid, ethylene glycol, hydroquinone, hydrobromic acid, hydroiodic acid.
In some preferred examples, the reaction temperature of the reflux reaction is 60 to 80 ℃, for example, 60 ℃, 62 ℃, 64 ℃, 66 ℃, 68 ℃,70 ℃, 72 ℃, 74 ℃, 76 ℃, 78 ℃ or 80 ℃, but the reflux reaction is not limited to the recited values, and other values not recited in the range of values are equally applicable.
In some preferred examples, the reaction time of the reflux reaction is 1-3h, and may be, for example, 1.0h, 1.2h, 1.4h, 1.6h, 1.8h, 2.0h, 2.2h, 2.4h, 2.6h, 2.8h, or 3.0h, although not limited to the recited values, other non-recited values within the range of values are equally applicable.
As a preferable technical scheme of the invention, in the step (II), the modified silicon nitride powder is prepared by adopting the following method:
And dispersing silicon nitride in a silane coupling agent solution to obtain a silicon nitride suspension, heating the silicon nitride suspension in a water bath, mechanically stirring, and sequentially carrying out centrifugal filtration, washing and drying on reactants after stirring to obtain the modified silicon nitride powder.
In some preferred examples, the silane coupling agent solution includes a silane coupling agent and a complex solvent, wherein the complex solvent is prepared by compounding ethanol and deionized water according to a volume ratio of (5-10): 1, and may be, for example, 5:1, 5.5:1, 6:1, 6.5:1, 7:1, 7.5:1, 8:1, 8.5:1, 9:1, 9.5:1 or 10:1, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
In some preferred examples, the mass fraction of the silane coupling agent in the silane coupling agent solution is 1 to 5wt%, for example, 1.0wt%, 1.5wt%, 2.0wt%, 2.5wt%, 3.0wt%, 3.5wt%, 4.0wt%, 4.5wt%, or 5.0wt%, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
In some preferred examples, the mass fraction of silicon nitride in the silicon nitride suspension is 1-10wt%, such as 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, or 10wt%, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
In some preferred examples, the water bath heating temperature is 70-80 ℃, for example, 70 ℃, 71 ℃, 72 ℃, 73 ℃, 74 ℃, 75 ℃, 76 ℃, 77 ℃, 78 ℃, 79 ℃ or 80 ℃, but is not limited to the recited values, and other non-recited values within the range are equally applicable.
In some preferred examples, the mechanical stirring speed is 800-1000r/min, for example 800r/min, 820r/min, 840r/min, 860r/min, 880r/min, 900r/min, 920r/min, 940r/min, 960r/min, 980r/min or 1000r/min, but not limited to the recited values, other non-recited values within the range of values are equally applicable.
In some preferred examples, the mechanical agitation is for a period of time ranging from 5 to 10 hours, such as, but not limited to, 5.0 hours, 5.5 hours, 6.0 hours, 6.5 hours, 7.0 hours, 7.5 hours, 8.0 hours, 8.5 hours, 9.0 hours, 9.5 hours, or 10.0 hours, although other non-recited values within this range of values are equally applicable.
In the step (ii), the stirring mode is ultrasonic stirring.
In some preferred examples, the ultrasonic power of the ultrasonic agitation is 500-1000W, and may be 500W, 550W, 600W, 650W, 700W, 750W, 800W, 850W, 900W, 950W, or 1000W, for example, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
In some preferred examples, the time of the ultrasonic agitation is 10-15min, for example, 10min, 10.5min, 11min, 11.5min, 12min, 12.5min, 13min, 13.5min, 14min, 14.5min or 15min, but not limited to the recited values, and other non-recited values within the range are equally applicable.
In a preferred embodiment of the present invention, in the step (iii), the stirring means is mechanical stirring.
In some preferred examples, the mechanical stirring speed is 800-1000r/min, for example 800r/min, 820r/min, 840r/min, 860r/min, 880r/min, 900r/min, 920r/min, 940r/min, 960r/min, 980r/min or 1000r/min, but not limited to the recited values, other non-recited values within the range of values are equally applicable.
In some preferred examples, the temperature of the stirring is 15-20min, for example, 15min, 15.5min, 16min, 16.5min, 17min, 17.5min, 18min, 18.5min, 19min, 19.5min or 20min, but is not limited to the recited values, and other non-recited values within the range are equally applicable.
The invention provides a preparation method of a lightweight grounding material compounded by graphene and fluorocarbon resin, which specifically comprises the following steps:
(1) Preparing modified graphene:
(1.1) dispersing graphene oxide in deionized water, and performing ultrasonic dispersion to obtain graphene oxide dispersion liquid;
Adding a hydroxyl modifier into graphene oxide dispersion liquid, continuously stirring, carrying out hydroxylation modification on graphene oxide to obtain a reaction product, wherein the mass ratio of the graphene oxide to the hydroxyl modifier is (10-20), and washing and filtering the reaction product to obtain a filter cake;
(1.3) dispersing the filter cake in a solvent to obtain a suspension, adding a reducing agent into the suspension, wherein the mass ratio of graphene oxide to the reducing agent is 1 (1-1.5), carrying out reflux reaction at 60-80 ℃ for 1-3h, and carrying out centrifugal filtration, washing and drying on a reaction product after the reaction is finished to obtain modified graphene;
(2) Preparing modified silicon nitride powder:
(2.1) dispersing silicon nitride in a silane coupling agent solution with the mass fraction of 1-5wt% to obtain silicon nitride suspension, wherein the silane coupling agent solution comprises a silane coupling agent and a composite solvent (the volume ratio of ethanol to deionized water is (5-10): 1); the mass fraction of silicon nitride in the silicon nitride suspension is 1-10wt%;
(2.2) heating the silicon nitride suspension in a water bath at 70-80 ℃, simultaneously mechanically stirring the silicon nitride suspension for 5-10h at the rotating speed of 800-1000r/min, and sequentially centrifugally filtering, washing and drying reactants to obtain modified silicon nitride powder;
(3) Preparing a resin emulsion:
Mixing 40-60 parts of fluorocarbon resin, 1-5 parts of defoamer and 1-5 parts of flatting agent according to a proportion, and stirring at a rotating speed of 600-800r/min for 5-10min to uniformly mix the components to obtain resin emulsion;
(4) Preparing a dispersion solution:
Mixing 0.5-1.5 parts of nanocellulose with 10-20 parts of solvent to obtain nanocellulose solution, dispersing 2-5 parts of modified graphene obtained in the step (1) and 1-5 parts of modified silicon nitride powder obtained in the step (2) in the nanocellulose solution, and performing ultrasonic dispersion for 10-15min under ultrasonic power of 500-1000W to obtain dispersion solution;
(5) Preparing a lightweight grounding material:
Mixing the resin emulsion obtained in the step (3) with the dispersion solution obtained in the step (4), stirring for 15-20min at 800-1000r/min to obtain the anti-corrosion conductive coating, uniformly coating the anti-corrosion conductive coating on the surface of the copper stranded wire, and drying to form the anti-corrosion conductive coating on the surface of the copper stranded wire to obtain the lightweight grounding material.
The anticorrosive heat-conducting coating provided by the invention is especially suitable for copper stranded wires, the conventional copper stranded wires comprise an inner core, the inner core is formed by stranding a plurality of copper wires, and the outer surface of the inner core is further coated with an insulating layer, a corrosion-resistant layer and a waterproof layer from inside to outside in sequence. The anti-corrosion heat-conducting coating provided by the invention can be coated on the surface of a single copper wire and/or filled in the twisted gaps among the copper wires, and the anti-corrosion heat-conducting coating formed after drying can effectively protect the copper wires and the copper stranded wires.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, the anti-corrosion conductive coating is formed on the surface of the metal matrix, the anti-corrosion conductive coating takes fluorocarbon resin as a matrix, and modified graphene, modified silicon nitride powder and nanocellulose are added, so that the overall wear resistance, heat conduction and mechanical properties of the grounding material can be greatly improved.
The anticorrosive conductive coating takes fluorocarbon resin as a matrix, and modified graphene is added, so that the modified graphene has extremely high heat conductivity and a special two-dimensional lamellar structure, can be used as an enhancement phase and a lubrication phase in the fluorocarbon resin matrix at the same time, and obviously improves the heat conductivity and wear resistance of the anticorrosive conductive coating. On one hand, the modified graphene has excellent heat conduction performance, so that friction heat generated at a friction interface can be timely conducted out in the friction and abrasion process of the grounding material, and the thermal damage to the grounding material due to high temperature is reduced; on the other hand, the modified graphene is a two-dimensional lamellar nano material, so that the modified graphene has an excellent interlayer sliding effect, is an ideal lubricating additive, and can improve the wear resistance of the anti-corrosion conductive coating.
According to the invention, the modified silicon nitride powder is also added into the fluorocarbon resin matrix, and can be dispersed on the surface and between the sheets of the modified graphene, so that the interlayer spacing between the sheets of the modified graphene is increased; meanwhile, the modified graphene also provides nucleation sites for the modified silicon nitride, so that the dispersibility of the modified silicon nitride is further improved. In addition, the modified silicon nitride powder fills up the defects of gaps, holes and the like in the fluorocarbon resin matrix to a certain extent, reduces the stress concentration phenomenon in the fluorocarbon resin matrix, and ensures that the prepared grounding material is not easy to generate brittle fracture.
Cellulose is a natural renewable biomass polymer material, and has the advantages of wide source, high thermal stability, biodegradability and the like. Nanocellulose is a nanoscale cellulose that can be divided into cellulose nanocrystals and cellulose nanofibers. The invention preferably adopts the cellulose nanofiber with the fibrillar structure with high length-diameter ratio, has the advantages of excellent mechanical property, light weight, high strength and the like, and the prepared grounding material can have the characteristics of light weight, high strength by being doped into the light weight grounding material. In addition, the nanocellulose can form a continuous network structure around the modified graphene and the modified silicon nitride powder under the action of natural force, so that the filler can be uniformly dispersed and spread, and therefore, the nanocellulose can be used as a stable dispersing agent for the modified graphene and the modified silicon nitride powder, and the dispersing effect of the modified graphene and the modified silicon nitride powder in a fluorocarbon resin matrix is remarkably improved. Meanwhile, the cellulose nanofiber is used as a long-chain fibrous nanomaterial, fiber filaments can be mutually interwoven to generate physical winding, the cellulose nanofiber can be used as a structural support material in a fluorocarbon resin matrix, and when the cellulose nanofiber is dispersed in a solvent, sol with a three-dimensional network structure can be formed, and the structure can promote the infiltration of fluorocarbon resin emulsion on one hand, so that the effective contact area between the fluorocarbon resin matrix and nanocellulose is improved, and the stress conduction in an anti-corrosion conductive coating is facilitated; on the other hand, a plurality of mutually communicated heat conduction passages exist in the three-dimensional network structure formed by physically crossing and winding the nanocellulose, a three-dimensional filler framework is constructed, modified graphene and modified silicon nitride powder can be attached to the surface of the heat conduction passages, and the structure enables a higher heat conduction coefficient to be achieved by adopting a lower-content filler.
Drawings
FIG. 1 is a flow chart of a process for preparing lightweight grounding materials according to embodiments 1-11 of the present invention;
FIG. 2 is a scanning electron microscope image of nanocellulose;
FIG. 3 is a scanning electron microscope image of nanocellulose in the dispersion solution provided in example 1;
FIG. 4 is an infrared spectrum of nanocellulose and the dispersion solution provided in example 1;
Fig. 5 is a cross-sectional scanning electron microscope image of the anticorrosive heat conducting coating provided in embodiment 1 of the invention.
Detailed Description
The technical scheme of the application is described in detail below with reference to specific embodiments and attached drawings. The examples described herein are specific embodiments of the present application for illustrating the concept of the present application; the description is intended to be illustrative and exemplary in nature and should not be construed as limiting the scope of the application in its aspects. In addition to the embodiments described herein, those skilled in the art can adopt other obvious solutions based on the disclosure of the claims and the specification thereof, including those adopting any obvious substitutions and modifications to the embodiments described herein.
Example 1
The embodiment provides a preparation method of a lightweight grounding material compounded by graphene and fluorocarbon resin, as shown in fig. 1, the preparation method specifically comprises the following steps:
(1) Preparing modified graphene:
(1.1) dispersing graphene oxide in deionized water, and performing ultrasonic dispersion to obtain graphene oxide dispersion liquid;
(1.2) adding triethanolamine into graphene oxide dispersion liquid, continuously stirring, carrying out hydroxylation modification on graphene oxide to obtain a reaction product, wherein the mass ratio of the graphene oxide to the triethanolamine is 1:10, and washing and filtering the reaction product to obtain a filter cake;
(1.3) dispersing the filter cake in deionized water to obtain a suspension, adding sodium borohydride into the suspension, carrying out reflux reaction for 3 hours at 60 ℃ with the mass ratio of graphene oxide to sodium borohydride being 1:1, and carrying out centrifugal filtration, washing and drying on a reaction product after the reaction is finished to obtain modified graphene;
(2) Preparing modified silicon nitride powder:
(2.1) dispersing silicon nitride in KH550 solution with the mass fraction of 1wt% to obtain silicon nitride suspension, wherein the KH550 solution comprises KH550 and a compound solvent (the volume ratio of ethanol to deionized water is 5:1); the mass fraction of silicon nitride in the silicon nitride suspension is 1wt%;
(2.2) heating the silicon nitride suspension in a water bath at 70 ℃, mechanically stirring the silicon nitride suspension for 10 hours at the rotating speed of 800r/min, and sequentially centrifugally filtering, washing and drying reactants to obtain modified silicon nitride powder;
(3) Preparing a resin emulsion:
Mixing 40 parts of fluorocarbon resin, 1 part of organic siloxane defoamer and 1 part of diacetone alcohol in proportion, and stirring at 600r/min for 10min to uniformly mix the components to obtain resin emulsion;
(4) Preparing a dispersion solution:
Mixing 0.5 part of cellulose nanofiber with 10 parts of deionized water to obtain a cellulose nanofiber solution, dispersing 2 parts of modified graphene obtained in the step (1) and 1 part of modified silicon nitride powder obtained in the step (2) in the cellulose nanofiber solution, and performing ultrasonic dispersion for 15min under 500W of ultrasonic power to obtain a dispersion solution;
(5) Preparing a lightweight grounding material:
mixing the resin emulsion obtained in the step (3) with the dispersion solution obtained in the step (4), stirring for 20min at 800r/min to obtain the anti-corrosion conductive coating, uniformly coating the anti-corrosion conductive coating on the surface of the copper stranded wire, and forming the anti-corrosion conductive coating on the surface of the copper stranded wire after drying to obtain the lightweight grounding material.
Fig. 2 is a scanning electron microscope image of original nanocellulose, and as can be seen from fig. 2, pits and cracks appear on the surface of the nanocellulose after the heat soaking treatment of sodium hydroxide solution, which is favorable for the deposition and adhesion of the modified graphene and modified silicon nitride powder on the surface of the nanocellulose. Fig. 3 is a scanning electron microscope image of nanocellulose in the dispersion solution prepared in this example, and as can be seen from comparison of fig. 2 and fig. 3, the nanocellulose surface is loaded with modified graphene and modified silicon nitride powder.
Fig. 4 is an infrared spectrum of the dispersion solution provided in the nanocellulose and example 1, and it can be seen from fig. 4 that the stretching vibration peak of hydroxyl group is stretching of the corresponding aromatic ring at 3440cm -1,3133cm-1, stretching vibration of alkane of methyl group and alkane of methylene group, and the absorption peaks appearing at 1645cm -1 and 1627cm -1 are caused by stretching vibration of C-H on saturated carbon atom after water absorption of nanocellulose. The nanocellulose deposit in the dispersion solution, compared to untreated nanocellulose, attached modified graphene and modified silicon nitride powder, an asymmetric stretching vibration peak of Si-O-C appears at 951cm -1. Si-O-Si covalent bonds from silanol autopolymerization occur at 788cm -1.
Fig. 5 is a cross-sectional scanning electron microscope image of the anticorrosion heat-conducting coating provided in embodiment 1 of the invention, and as can be seen from fig. 5, grooves and rows of fluorocarbon resin matrix can be observed after the fibers are pulled out, which indicates that the interfacial compatibility between nanocellulose and fluorocarbon resin matrix is significantly improved.
Example 2
The embodiment provides a preparation method of a lightweight grounding material compounded by graphene and fluorocarbon resin, as shown in fig. 1, the preparation method specifically comprises the following steps:
(1) Preparing modified graphene:
(1.1) dispersing graphene oxide in deionized water, and performing ultrasonic dispersion to obtain graphene oxide dispersion liquid;
(1.2) adding polyvinyl alcohol into graphene oxide dispersion liquid, continuously stirring, carrying out hydroxylation modification on graphene oxide to obtain a reaction product, wherein the mass ratio of the graphene oxide to the polyvinyl alcohol is 1:12, and washing and filtering the reaction product to obtain a filter cake;
(1.3) dispersing the filter cake in ethanol to obtain a suspension, adding ascorbic acid into the suspension, carrying out reflux reaction for 2.5 hours at 65 ℃ with the mass ratio of graphene oxide to ascorbic acid being 1:1.1, and carrying out centrifugal filtration, washing and drying on a reaction product after the reaction is finished to obtain modified graphene;
(2) Preparing modified silicon nitride powder:
(2.1) dispersing silicon nitride in a KH550 solution with the mass fraction of 2wt% to obtain a silicon nitride suspension, wherein the KH550 solution comprises KH550 and a compound solvent (the volume ratio of ethanol to deionized water is 6:1); the mass fraction of silicon nitride in the silicon nitride suspension was 3wt%;
(2.2) heating the silicon nitride suspension in a water bath at 72 ℃, mechanically stirring the silicon nitride suspension for 9 hours at a rotating speed of 850r/min, and sequentially centrifugally filtering, washing and drying reactants to obtain modified silicon nitride powder;
(3) Preparing a resin emulsion:
mixing 45 parts of fluorocarbon resin, 2 parts of organic siloxane defoamer and 2 parts of isophorone in proportion, and stirring at a rotating speed of 650r/min for 8min to uniformly mix the components to obtain resin emulsion;
(4) Preparing a dispersion solution:
Mixing 0.8 part of cellulose nanofiber with 12 parts of ethanol to obtain a cellulose nanofiber solution, dispersing 3 parts of modified graphene obtained in the step (1) and 2 parts of modified silicon nitride powder obtained in the step (2) in the cellulose nanofiber solution, and performing ultrasonic dispersion for 13min under the ultrasonic power of 600W to obtain a dispersion solution;
(5) Preparing a lightweight grounding material:
Mixing the resin emulsion obtained in the step (3) with the dispersion solution obtained in the step (4), stirring for 19min at 850r/min to obtain the anti-corrosion conductive coating, uniformly coating the anti-corrosion conductive coating on the surface of the copper stranded wire, and forming the anti-corrosion conductive coating on the surface of the copper stranded wire after drying to obtain the lightweight grounding material.
Example 3
The embodiment provides a preparation method of a lightweight grounding material compounded by graphene and fluorocarbon resin, as shown in fig. 1, the preparation method specifically comprises the following steps:
(1) Preparing modified graphene:
(1.1) dispersing graphene oxide in deionized water, and performing ultrasonic dispersion to obtain graphene oxide dispersion liquid;
(1.2) adding triisopropanolamine into graphene oxide dispersion liquid, continuously stirring, carrying out hydroxylation modification on graphene oxide to obtain a reaction product, wherein the mass ratio of the graphene oxide to the triisopropanolamine is 1:15, and washing and filtering the reaction product to obtain a filter cake;
(1.3) dispersing a filter cake in n-propanol to obtain a suspension, adding hydrazine hydrate into the suspension, carrying out reflux reaction for 2 hours at 70 ℃ with the mass ratio of graphene oxide to the hydrazine hydrate being 1:1.2, and carrying out centrifugal filtration, washing and drying on a reaction product after the reaction is finished to obtain modified graphene;
(2) Preparing modified silicon nitride powder:
(2.1) dispersing silicon nitride in a KH560 solution with the mass fraction of 3wt% to obtain a silicon nitride suspension, wherein the KH560 solution comprises KH560 and a compound solvent (the volume ratio of ethanol to deionized water is 8:1); the mass fraction of silicon nitride in the silicon nitride suspension is 5wt%;
(2.2) heating the silicon nitride suspension in a water bath at 75 ℃, mechanically stirring the silicon nitride suspension for 8 hours at the rotating speed of 900r/min, and sequentially centrifugally filtering, washing and drying reactants to obtain modified silicon nitride powder;
(3) Preparing a resin emulsion:
50 parts of fluorocarbon resin, 3 parts of mineral oil defoamer and 3 parts of acrylic ester are mixed according to a proportion, and stirred for 7 minutes at a rotating speed of 700r/min, so that the components are uniformly mixed to obtain resin emulsion;
(4) Preparing a dispersion solution:
Mixing 1 part of cellulose nanofiber with 15 parts of n-propanol to obtain a cellulose nanofiber solution, dispersing 3 parts of modified graphene obtained in the step (1) and 3 parts of modified silicon nitride powder obtained in the step (2) in the cellulose nanofiber solution, and performing ultrasonic dispersion for 12min under the ultrasonic power of 800W to obtain a dispersion solution;
(5) Preparing a lightweight grounding material:
Mixing the resin emulsion obtained in the step (3) with the dispersion solution obtained in the step (4), stirring for 18min at 900r/min to obtain the anti-corrosion conductive coating, uniformly coating the anti-corrosion conductive coating on the surface of the copper stranded wire, and forming the anti-corrosion conductive coating on the surface of the copper stranded wire after drying to obtain the lightweight grounding material.
Example 4
The embodiment provides a preparation method of a lightweight grounding material compounded by graphene and fluorocarbon resin, as shown in fig. 1, the preparation method specifically comprises the following steps:
(1) Preparing modified graphene:
(1.1) dispersing graphene oxide in deionized water, and performing ultrasonic dispersion to obtain graphene oxide dispersion liquid;
(1.2) adding N-methyldiethanolamine into graphene oxide dispersion liquid, continuously stirring, carrying out hydroxylation modification on graphene oxide to obtain a reaction product, wherein the mass ratio of the graphene oxide to the N-methyldiethanolamine is 1:18, and washing and filtering the reaction product to obtain a filter cake;
(1.3) dispersing a filter cake in isopropanol to obtain a suspension, adding ethylene glycol into the suspension, carrying out reflux reaction for 1.5 hours at 75 ℃, and carrying out centrifugal filtration, washing and drying on a reaction product after the reaction is finished to obtain modified graphene, wherein the mass ratio of graphene oxide to ethylene glycol is 1:1.3;
(2) Preparing modified silicon nitride powder:
(2.1) dispersing silicon nitride in a KH570 solution with the mass fraction of 4wt% to obtain a silicon nitride suspension, wherein the KH570 solution comprises KH570 and a compound solvent (the volume ratio of ethanol to deionized water is 9:1); the mass fraction of silicon nitride in the silicon nitride suspension was 7wt%;
(2.2) heating the silicon nitride suspension in a water bath at 78 ℃, mechanically stirring the silicon nitride suspension for 6 hours at a rotating speed of 950r/min, and sequentially centrifugally filtering, washing and drying reactants to obtain modified silicon nitride powder;
(3) Preparing a resin emulsion:
Mixing 55 parts of fluorocarbon resin, 4 parts of polyether defoamer and 4 parts of polyether siloxane in proportion, and stirring at a rotating speed of 750r/min for 6min to uniformly mix the components to obtain resin emulsion;
(4) Preparing a dispersion solution:
Mixing 1.2 parts of cellulose nanofiber with 18 parts of isopropanol to obtain a cellulose nanofiber solution, dispersing 4 parts of modified graphene obtained in the step (1) and 4 parts of modified silicon nitride powder obtained in the step (2) in the cellulose nanofiber solution, and performing ultrasonic dispersion for 11min under 900W of ultrasonic power to obtain a dispersion solution;
(5) Preparing a lightweight grounding material:
Mixing the resin emulsion obtained in the step (3) with the dispersion solution obtained in the step (4), stirring for 16min at 950r/min to obtain the anti-corrosion conductive coating, uniformly coating the anti-corrosion conductive coating on the surface of the copper stranded wire, and forming the anti-corrosion conductive coating on the surface of the copper stranded wire after drying to obtain the lightweight grounding material.
Example 5
The embodiment provides a preparation method of a lightweight grounding material compounded by graphene and fluorocarbon resin, which specifically comprises the following steps:
(1) Preparing modified graphene:
(1.1) dispersing graphene oxide in deionized water, and performing ultrasonic dispersion to obtain graphene oxide dispersion liquid;
(1.2) adding triethanolamine into graphene oxide dispersion liquid, continuously stirring, carrying out hydroxylation modification on graphene oxide to obtain a reaction product, wherein the mass ratio of the graphene oxide to the triethanolamine is 1:20, and washing and filtering the reaction product to obtain a filter cake;
(1.3) dispersing a filter cake in n-butanol to obtain a suspension, adding hydrobromic acid into the suspension, carrying out reflux reaction for 1h at 80 ℃ with the mass ratio of graphene oxide to hydrobromic acid being 1:1.5, and carrying out centrifugal filtration, washing and drying on a reaction product after the reaction is finished to obtain modified graphene;
(2) Preparing modified silicon nitride powder:
(2.1) dispersing silicon nitride in a KH570 solution with the mass fraction of 5wt% to obtain a silicon nitride suspension, wherein the KH570 solution comprises KH570 and a compound solvent (the volume ratio of ethanol to deionized water is 10:1); the mass fraction of silicon nitride in the silicon nitride suspension was 10wt%;
(2.2) heating the silicon nitride suspension in a water bath at 80 ℃, simultaneously mechanically stirring the silicon nitride suspension for 5 hours at a rotating speed of 1000r/min, and sequentially centrifugally filtering, washing and drying reactants to obtain modified silicon nitride powder;
(3) Preparing a resin emulsion:
Mixing 60 parts of fluorocarbon resin, 5 parts of polyether defoamer and 5 parts of polydimethylsiloxane in proportion, and stirring at a speed of 800r/min for 5min to uniformly mix the components to obtain resin emulsion;
(4) Preparing a dispersion solution:
Mixing 1.5 parts of cellulose nanofiber with 20 parts of n-butanol to obtain a cellulose nanofiber solution, dispersing 5 parts of modified graphene obtained in the step (1) and 5 parts of modified silicon nitride powder obtained in the step (2) in the cellulose nanofiber solution, and performing ultrasonic dispersion for 10min under ultrasonic power of 1000W to obtain a dispersion solution;
(5) Preparing a lightweight grounding material:
Mixing the resin emulsion obtained in the step (3) with the dispersion solution obtained in the step (4), stirring for 15min at 1000r/min to obtain the anti-corrosion conductive coating, uniformly coating the anti-corrosion conductive coating on the surface of the copper stranded wire, and forming the anti-corrosion conductive coating on the surface of the copper stranded wire after drying to obtain the lightweight grounding material.
Example 6
The present embodiment provides a preparation method of a lightweight grounding material compounded by graphene and fluorocarbon resin, which is different from embodiment 1 in that the addition amount of cellulose nanofibers in step (4) is adjusted to 0.1 weight part, and other process conditions and operation steps are identical to those of embodiment 1.
Example 7
The present embodiment provides a method for preparing a lightweight grounding material by compounding graphene and fluorocarbon resin, which is different from embodiment 1 in that the addition amount of cellulose nanofibers in step (4) is adjusted to 2 parts by weight, and other process conditions and operation steps are identical to those of embodiment 1.
Example 8
The present embodiment provides a method for preparing a lightweight grounding material by compounding graphene and fluorocarbon resin, which is different from embodiment 1 in that the addition amount of modified graphene in step (4) is adjusted to 1 part by weight, and other process conditions and operation steps are identical to those of embodiment 1.
Example 9
The present embodiment provides a method for preparing a lightweight grounding material by compounding graphene and fluorocarbon resin, which is different from embodiment 1 in that the addition amount of modified graphene in step (4) is adjusted to 8 parts by weight, and other process conditions and operation steps are identical to those of embodiment 1.
Example 10
The present example provides a preparation method of a lightweight grounding material compounded by graphene and fluorocarbon resin, which is different from example 1 in that the addition amount of the modified silicon nitride powder in step (4) is adjusted to 0.5 parts by weight, and other process conditions and operation steps are exactly the same as example 1.
Example 11
The present example provides a method for preparing a lightweight grounding material by compounding graphene with fluorocarbon resin, which is different from example 1 in that the addition amount of the modified silicon nitride powder in step (4) is adjusted to 8 parts by weight, and other process conditions and operation steps are exactly the same as example 1.
Comparative example
The comparative example provides a preparation method of a grounding material, which specifically comprises the following steps:
mixing 40 parts of fluorocarbon resin, 1 part of organosiloxane defoamer and 1 part of diacetone alcohol in proportion, stirring for 10min at a rotating speed of 600r/min to uniformly mix the components to obtain a coating, uniformly coating the coating on the surface of a copper stranded wire, and forming a coating on the surface of the copper stranded wire after drying to obtain the lightweight grounding material.
The grounding materials provided in examples 1-11 and comparative examples were tested for impact strength, thermal conductivity and corrosion resistance, as follows:
(2) Impact strength: the impact strength of the grounding material is tested by referring to the national standard GB/T33835-2017 method for testing impact strength of Friction Material.
(3) Thermal conductivity coefficient: the thermal conductivity of the coating of the grounding material was tested with reference to the national standard GB/T10297-2015 "measurement hotline method of thermal conductivity of non-metallic solid materials".
(3) Acid and alkali corrosion resistance test: the grounding material is processed into a sample with phi of 30mm multiplied by 4mm, the weight of the sample is weighed, the sample is soaked in 40wt% NaOH solution and boiled for 100 hours at high temperature, then the weight of the sample is weighed again, and the alkali-resistant weight loss is calculated by subtracting the weights before and after the sample is soaked. The weight of the sample is weighed again after the sample is soaked in 30wt% hydrochloric acid solution for 400 hours at normal temperature, and the acid-resistant weight loss is calculated by subtracting the weights before and after the sample is soaked.
The test results are shown in Table 1.
Table 1 results of performance testing of the ground materials provided in examples 1-11 and comparative examples
As can be seen from the test results provided in table 1, the impact strength and the thermal conductivity of the grounding materials prepared in examples 1 to 5 of the present invention are higher than those of the comparative examples, which indicates that the thermal conductivity and the mechanical properties of the grounding materials can be effectively improved by doping the fluorocarbon resin with the modified graphene, the modified silicon nitride powder and the nanocellulose. In addition, the alkali resistance weight loss and the acid resistance weight loss of the grounding materials prepared in the embodiments 1 to 5 are lower than those of the comparative examples, which shows that the lightweight grounding materials prepared in the invention have excellent corrosion resistance.
As can be seen from the test results provided in examples 1, 6 and 7, the impact strength and thermal conductivity of the grounding material formed in example 6 were lower than those of example 1, because the weight part of cellulose nanofibers added in example 6 was too low to form a complete and sufficient number of thermal conduction channels, thereby resulting in ineffective adhesion of the modified graphene and the modified silicon nitride powder. The impact strength and thermal conductivity of the grounding material formed in example 7 are lower than those of example 1, because the excessive weight portion of cellulose nanofibers added in example 7 aggravates the aggregation phenomenon of cellulose nanofibers, a three-dimensional network structure with sufficient pore channels cannot be formed, the number and penetration degree of the thermal conduction channels are further affected, and meanwhile, serious stress concentration phenomenon in the grounding material is caused due to the aggregation of cellulose nanofibers.
As can be seen from the test results provided in examples 1,8 and 9, the thermal conductivity of the grounding material formed in example 8 is lower than that in example 1, and the alkali-resistant weight loss and acid-resistant weight loss are higher than those in example 1, because the modified graphene mainly plays a role in improving the thermal conductivity and corrosion resistance in the grounding material, while the weight part of the modified graphene added in example 8 is too low, resulting in that the modified graphene cannot sufficiently exert its reinforcing effect. The impact strength of the grounding material formed in example 9 is lower than that of example 1, because the excessive weight portion of the modified graphene added in example 9 causes serious agglomeration of the modified graphene in the fluorocarbon resin matrix, so that serious stress concentration occurs in the grounding material, crack growth is easy to occur, and the impact strength of the grounding material is affected.
As can be seen from the test results provided in examples 1, 10 and 11, the impact strength of the grounding material formed in example 10 is lower than that in example 1, because the modified silicon nitride powder added in example 10 is too low in weight portion to effectively fill the defects such as voids and holes in the fluorocarbon resin matrix, so that stress concentration is likely to occur in the grounding material, and the impact strength of the grounding material is further affected. The impact strength of the grounding material formed in example 11 is lower than that of example 1, because the excessive weight of the modified silicon nitride powder added in example 11 causes serious agglomeration of the modified graphene in the fluorocarbon resin matrix, so that serious stress concentration occurs in the grounding material, crack growth is easy to occur, and impact strength of the grounding material is affected.
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.
Claims (10)
1. The lightweight grounding material is characterized by comprising a metal matrix and an anti-corrosion conductive coating coated on the surface of the metal matrix;
the anticorrosion conductive coating comprises fluorocarbon resin, modified graphene, modified silicon nitride powder, nanocellulose, a defoaming agent, a leveling agent and a solvent.
2. The lightweight grounding material compounded by graphene and fluorocarbon resin according to claim 1, wherein the corrosion-resistant conductive coating comprises the following components in parts by weight:
40-60 parts of fluorocarbon resin;
2-5 parts of modified graphene;
1-5 parts of modified silicon nitride powder;
0.5-1.5 parts of nanocellulose;
1-5 parts of a defoaming agent;
1-5 parts of flatting agent;
10-20 parts of solvent.
3. The lightweight grounding material composited by graphene and fluorocarbon resin according to claim 1, wherein the defoaming agent is any one or a combination of at least two of organosiloxane defoaming agents, mineral oil defoaming agents and polyether defoaming agents;
the leveling agent is any one or a combination of at least two of diacetone alcohol, isophorone, acrylic ester, polyether siloxane and polydimethylsiloxane;
The solvent is any one or the combination of at least two of deionized water, ethanol, n-propanol, isopropanol, n-butanol, isobutanol and tertiary butanol.
4. A method for preparing the lightweight grounding material composited by graphene and fluorocarbon resin as claimed in any one of claims 1 to 3, wherein the preparation method comprises the following steps:
Mixing fluorocarbon resin, a defoaming agent and a leveling agent in proportion, and uniformly stirring to obtain resin emulsion;
(II) mixing nanocellulose with a solvent in proportion to obtain a nanocellulose solution, dispersing modified graphene and modified silicon nitride powder in the nanocellulose solution, and uniformly stirring to obtain a dispersion solution;
And (III) mixing the resin emulsion obtained in the step (I) with the dispersion solution obtained in the step (II), uniformly stirring to obtain an anti-corrosion conductive coating, coating the anti-corrosion conductive coating on the surface of a metal matrix, and drying to obtain the lightweight grounding material compounded by the graphene and fluorocarbon resin.
5. The method for preparing a lightweight grounding material composited by graphene and fluorocarbon resin as claimed in claim 4, wherein in the step (i), the stirring mode is mechanical stirring;
the rotating speed of the mechanical stirring is 600-800r/min;
the mechanical stirring time is 5-10min.
6. The method for preparing a lightweight grounding material composited by graphene and fluorocarbon resin as claimed in claim 4, wherein in the step (ii), the modified graphene is prepared by the following method:
(1) Dispersing graphene oxide in deionized water, and performing ultrasonic dispersion to obtain graphene oxide dispersion liquid;
(2) Adding a hydroxyl modifier into the graphene oxide dispersion liquid, continuously stirring, carrying out hydroxylation modification on graphene oxide to obtain a reaction product, and washing and filtering the reaction product to obtain a filter cake;
(3) Dispersing the filter cake in a solvent to obtain a suspension, adding a reducing agent into the suspension for reflux reaction, and centrifugally filtering, washing and drying the reaction product after the reaction is finished to obtain the modified graphene.
7. The method for preparing a lightweight grounding material composited by graphene and fluorocarbon resin according to claim 6, wherein in the step (2), the hydroxyl modifier is any one or a combination of at least two of triethanolamine, polyvinyl alcohol, triisopropanolamine and N-methyldiethanolamine;
The mass ratio of the graphene oxide to the hydroxyl modifier is 1 (10-20);
In the step (3), the mass ratio of the graphene oxide to the reducing agent is 1 (1-1.5);
The reducing agent is any one or the combination of at least two of hydrazine hydrate, sodium borohydride, glucose, ascorbic acid, ethylene glycol, hydroquinone, hydrobromic acid and hydroiodic acid;
the reaction temperature of the reflux reaction is 60-80 ℃;
the reaction time of the reflux reaction is 1-3h.
8. The method for preparing a lightweight grounding material composited by graphene and fluorocarbon resin as claimed in claim 4, wherein in the step (ii), the modified silicon nitride powder is prepared by the following method:
Dispersing silicon nitride in a silane coupling agent solution to obtain a silicon nitride suspension, heating the silicon nitride suspension in a water bath, mechanically stirring, and sequentially centrifugally filtering, washing and drying reactants after stirring to obtain modified silicon nitride powder;
the silane coupling agent solution comprises a silane coupling agent and a composite solvent, wherein the composite solvent is prepared by compounding ethanol and deionized water according to the volume ratio of (5-10): 1;
The mass fraction of the silane coupling agent in the silane coupling agent solution is 1-5wt%;
the mass fraction of silicon nitride in the silicon nitride suspension is 1-10wt%;
the temperature of the water bath heating is 70-80 ℃;
The rotating speed of the mechanical stirring is 800-1000r/min;
the time of the mechanical stirring is 5-10h.
9. The method for preparing a lightweight grounding material composited by graphene and fluorocarbon resin according to claim 4, wherein in the step (ii), the stirring mode is ultrasonic stirring;
the ultrasonic power of the ultrasonic stirring is 500-1000W;
the ultrasonic stirring time is 10-15min.
10. The method for preparing a lightweight grounding material composited by graphene and fluorocarbon resin as claimed in claim 4, wherein in the step (iii), the stirring mode is mechanical stirring;
The rotating speed of the mechanical stirring is 800-1000r/min;
The stirring temperature is 15-20min.
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Citations (5)
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| CN105819435A (en) * | 2016-04-27 | 2016-08-03 | 桂林电子科技大学 | In-situ modified reduced graphene oxide and preparation method thereof |
| CN106221396A (en) * | 2016-08-12 | 2016-12-14 | 德阳烯碳科技有限公司 | A kind of Graphene heat radiation coating and preparation method thereof |
| CN107033738A (en) * | 2017-05-04 | 2017-08-11 | 中国海洋大学 | A kind of preparation method of modified silicon nitride corrosion-inhibiting coating |
| CN110205021A (en) * | 2019-06-05 | 2019-09-06 | 常州烯源纳米科技有限公司 | Graphene heat-radiation anticorrosion paint, Its Preparation Method And Use |
| CN112159535A (en) * | 2020-09-29 | 2021-01-01 | 上海健康医学院 | Partially reduced graphene oxide-nanocellulose crystal-polyvinyl alcohol composite conductive hydrogel and preparation method and application thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105819435A (en) * | 2016-04-27 | 2016-08-03 | 桂林电子科技大学 | In-situ modified reduced graphene oxide and preparation method thereof |
| CN106221396A (en) * | 2016-08-12 | 2016-12-14 | 德阳烯碳科技有限公司 | A kind of Graphene heat radiation coating and preparation method thereof |
| CN107033738A (en) * | 2017-05-04 | 2017-08-11 | 中国海洋大学 | A kind of preparation method of modified silicon nitride corrosion-inhibiting coating |
| CN110205021A (en) * | 2019-06-05 | 2019-09-06 | 常州烯源纳米科技有限公司 | Graphene heat-radiation anticorrosion paint, Its Preparation Method And Use |
| CN112159535A (en) * | 2020-09-29 | 2021-01-01 | 上海健康医学院 | Partially reduced graphene oxide-nanocellulose crystal-polyvinyl alcohol composite conductive hydrogel and preparation method and application thereof |
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