CN117534996B - High-strength wear-resistant aluminum alloy template and surface treatment process thereof - Google Patents
High-strength wear-resistant aluminum alloy template and surface treatment process thereof Download PDFInfo
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- CN117534996B CN117534996B CN202311503014.0A CN202311503014A CN117534996B CN 117534996 B CN117534996 B CN 117534996B CN 202311503014 A CN202311503014 A CN 202311503014A CN 117534996 B CN117534996 B CN 117534996B
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- stirring
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- aluminum alloy
- heating
- room temperature
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- 229910000838 Al alloy Inorganic materials 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 30
- 230000008569 process Effects 0.000 title claims abstract description 27
- 238000004381 surface treatment Methods 0.000 title claims abstract description 25
- 238000000576 coating method Methods 0.000 claims abstract description 116
- 239000011248 coating agent Substances 0.000 claims abstract description 113
- 238000003756 stirring Methods 0.000 claims abstract description 104
- -1 furyl benzoxazine Chemical compound 0.000 claims abstract description 87
- 238000010438 heat treatment Methods 0.000 claims abstract description 65
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 61
- 230000007797 corrosion Effects 0.000 claims abstract description 61
- 238000005260 corrosion Methods 0.000 claims abstract description 61
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000003112 inhibitor Substances 0.000 claims abstract description 41
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 39
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 36
- 238000005507 spraying Methods 0.000 claims abstract description 30
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 24
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 24
- 239000000126 substance Substances 0.000 claims abstract description 21
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- 239000000377 silicon dioxide Substances 0.000 claims abstract description 18
- 239000002077 nanosphere Substances 0.000 claims abstract description 17
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims abstract description 16
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical class O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims abstract description 16
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- 238000007254 oxidation reaction Methods 0.000 claims abstract description 14
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- 238000006243 chemical reaction Methods 0.000 claims description 47
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 239000008367 deionised water Substances 0.000 claims description 26
- 229910021641 deionized water Inorganic materials 0.000 claims description 26
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 24
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 23
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- 239000003094 microcapsule Substances 0.000 claims description 20
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 18
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- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 17
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 17
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 16
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 16
- SNONAWYBSWWKSX-UHFFFAOYSA-N 2h-1,2-benzoxazin-3-ol Chemical compound C1=CC=C2ONC(O)=CC2=C1 SNONAWYBSWWKSX-UHFFFAOYSA-N 0.000 claims description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 13
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- 229920002866 paraformaldehyde Polymers 0.000 claims description 12
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 10
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 10
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- 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 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
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- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 8
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 8
- UCPYLLCMEDAXFR-UHFFFAOYSA-N triphosgene Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl UCPYLLCMEDAXFR-UHFFFAOYSA-N 0.000 claims description 8
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 7
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 7
- NTPBFFVFKCMDCG-UHFFFAOYSA-N CN(C=O)C.C(CCC)N Chemical compound CN(C=O)C.C(CCC)N NTPBFFVFKCMDCG-UHFFFAOYSA-N 0.000 claims description 6
- DDRPCXLAQZKBJP-UHFFFAOYSA-N furfurylamine Chemical compound NCC1=CC=CO1 DDRPCXLAQZKBJP-UHFFFAOYSA-N 0.000 claims description 6
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims description 6
- 229940012189 methyl orange Drugs 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- 229960000583 acetic acid Drugs 0.000 claims description 5
- 239000000908 ammonium hydroxide Substances 0.000 claims description 5
- 239000012362 glacial acetic acid Substances 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 2
- 125000002541 furyl group Chemical group 0.000 claims 1
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
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- 230000001070 adhesive effect Effects 0.000 description 8
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
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- MORZKHPHARBEJZ-UHFFFAOYSA-N 3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-octadecafluoro-2-(1,1,2,2,2-pentafluoroethyl)undec-2-enoic acid Chemical compound C(=C(C(C(C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)F)(C(=O)O)C(C(F)(F)F)(F)F MORZKHPHARBEJZ-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
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- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical group C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 description 3
- 238000005698 Diels-Alder reaction Methods 0.000 description 3
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- QUKRIOLKOHUUBM-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl prop-2-enoate Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCOC(=O)C=C QUKRIOLKOHUUBM-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
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- 230000007547 defect Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
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- YDKRMHZRTFEYTA-UHFFFAOYSA-N 3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,13,13,13-docosafluoro-2-(1,1,2,2,2-pentafluoroethyl)tridec-2-enoic acid Chemical compound C(=C(C(C(C(C(C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)F)(C(=O)O)C(C(F)(F)F)(F)F YDKRMHZRTFEYTA-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
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- 230000005489 elastic deformation Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
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- 230000002035 prolonged effect Effects 0.000 description 1
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- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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Classifications
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- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
- B05D1/38—Successively applying liquids or other fluent materials, e.g. without intermediate treatment with intermediate treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
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- B05D7/50—Multilayers
- B05D7/56—Three layers or more
- B05D7/58—No clear coat specified
- B05D7/586—No clear coat specified each layer being cured, at least partially, separately
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- 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
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- 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
- C09D127/18—Homopolymers or copolymers of tetrafluoroethene
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- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
- C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
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- 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
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- 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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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Abstract
The invention relates to the technical field of aluminum alloy templates, and discloses a high-strength wear-resistant aluminum alloy template and a surface treatment process thereof; the method comprises the following steps: adding the 2-mercaptobenzothiazole modified nano silica nanospheres into epoxy resin, and uniformly stirring to obtain a coating A; heating furyl benzoxazine modified siloxane and maleimide modified siloxane to 45-50 ℃, uniformly mixing, adding the mixture into N, N-dimethylformamide, uniformly stirring, and performing rotary evaporation to obtain a coating B; ultrasonically dispersing the corrosion inhibitor modified reduced graphene oxide in polytetrafluoroethylene resin to obtain a coating C; and (3) sequentially carrying out polishing pretreatment, sand blasting, chemical polishing, anodic oxidation, spray coating A, spray coating B and spray coating C on the surface of the aluminum alloy template, and heating and curing to obtain the high-strength wear-resistant aluminum alloy template.
Description
Technical Field
The invention relates to the technical field of aluminum alloy templates, in particular to a high-strength wear-resistant aluminum alloy template and a surface treatment process thereof.
Background
The aluminum alloy template is a novel template system, and the aluminum template is designed according to the modulus, can be freely combined according to different structural dimensions, is widely applied to the building industry, and greatly improves the construction efficiency of the building construction engineering. Under the condition of external force friction, the traditional wear-resistant aluminum alloy template can generate cracks and even peel off, so that the aluminum alloy template cannot be protected, and the aluminum alloy template cannot be protected due to corrosion of different acid and alkali mediums in the environment, so that the paint film is damaged, the aluminum alloy template cannot be protected, and the service life of the aluminum alloy template is reduced.
Therefore, the invention provides the high-strength wear-resistant aluminum alloy template and the surface treatment process thereof.
Disclosure of Invention
The invention aims to provide a high-strength wear-resistant aluminum alloy template and a surface treatment process thereof, so as to solve the problems in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme:
a surface treatment process of a high-strength wear-resistant aluminum alloy template comprises the following steps:
S1: adding polyvinylpyrrolidone into deionized water, stirring uniformly, adding styrene and potassium persulfate, heating to 70-75 ℃ and reacting for 24-26h to obtain polystyrene solution; adding polystyrene solution into ethanol, stirring uniformly, adding ammonium hydroxide and tetraethoxysilane, stirring at room temperature for reaction for 18-20h, centrifuging, filtering, washing, drying at room temperature, and performing heat treatment at 500-550 ℃ for 5-6h to obtain silica nanospheres; adding the silica nanospheres into an acetone solution of 2-mercaptobenzothiazole, stirring at room temperature for reaction for 36-40h, centrifuging, washing, and drying at 60-65 ℃ to obtain modified silica nanospheres; adding the modified nano silicon dioxide nanospheres into epoxy resin, and uniformly stirring to obtain a coating A;
s2: heating furyl benzoxazine modified siloxane and maleimide modified siloxane to 45-50 ℃, uniformly mixing, adding the mixture into N, N-dimethylformamide, uniformly stirring, and performing rotary evaporation to obtain a coating B;
S3: adding graphene oxide into deionized water, performing ultrasonic dispersion for 2-2.5h, adjusting the pH to 9-10, adding hydrazine hydrate, heating to 90-95 ℃ for reaction for 1-2h, adding a corrosion inhibitor microcapsule, heating to reflux for reaction for 4-6h, washing, and removing unreacted substances to obtain modified reduced graphene oxide; ultrasonically dispersing modified reduced graphene oxide in polytetrafluoroethylene resin to obtain a coating C;
S4: the surface of the aluminum alloy template is sequentially subjected to polishing pretreatment, sand blasting, chemical polishing, anodic oxidation, heating of the spray coating A to 90-95 ℃ for curing for 1.5-2h, heating of the spray coating B to 60-65 ℃ for pre-curing for 2-3h, and respectively curing of the spray coating C at 100 ℃, 110 ℃ and 120 ℃ for 2h to obtain the high-strength wear-resistant aluminum alloy template.
Further, the preparation method of the furyl benzoxazine modified siloxane comprises the following steps:
adding the diaminopropyl end-capped polydimethylsiloxane into tetrahydrofuran, uniformly stirring, adding 13.16mol/L-14.23mol/L formaldehyde solution under the conditions of nitrogen atmosphere and ice bath, stirring for 1-1.5h, adding catechol, heating to reflux reaction for 5-6h, performing rotary evaporation, extracting, washing and drying to obtain phenolic hydroxyl benzoxazine modified siloxane; adding paraformaldehyde into deionized water, adjusting pH to 8-9, heating to reflux and stirring until the paraformaldehyde is completely dissolved, cooling to room temperature, adding furfuryl amine and dioxane, stirring at room temperature for 1-1.5h, adding phenolic hydroxy benzoxazine modified siloxane, heating to reflux and stirring for 5-6h, extracting, washing and extracting to obtain furyl benzoxazine modified siloxane;
Further, the bis-aminopropyl terminated polydimethylsiloxane: formaldehyde solution: the mol ratio of catechol is 1:4 (2-3); the paraformaldehyde: bran amine: the mass ratio of the phenolic hydroxyl benzoxazine modified siloxane is 3.3 (4.85-5) to 3.9.
Further, the preparation method of the maleimide modified siloxane comprises the following steps:
Adding aminopropyl end-capped polydimethylsiloxane and maleic anhydride into glacial acetic acid, stirring for 2-2.5h at room temperature, heating to 140-145 ℃ for reaction for 6-6.5h, cooling, adding dichloromethane, standing, washing, drying, and removing solvent to obtain maleimide modified siloxane;
Further, the aminopropyl terminated polydimethylsiloxane: the molar ratio of maleic anhydride is 1 (8-9).
Further, the preparation method of the corrosion inhibitor microcapsule comprises the following steps:
Adding a corrosion inhibitor and methyl orange into deionized water, stirring for 5-6h at room temperature, adding ferric trichloride hexahydrate, stirring for 1-1.5h at room temperature, adding pyrrole, adjusting the pH to 8-9, stirring for 24-26h at room temperature, carrying out suction filtration, washing and drying to obtain a corrosion inhibitor microcapsule;
further, the corrosion inhibitor: ferric trichloride hexahydrate: the mass ratio of the pyrrole is 1 (6-9): 2.
Further, the preparation method of the corrosion inhibitor comprises the following steps:
adding L-cysteine into deionized water, stirring uniformly, regulating the pH to 7.3-7.5, adding perfluoro-acrylic ester, stirring at room temperature for reaction for 16-20h, adding ethanol for precipitation, washing, filtering and drying to obtain an intermediate A; adding the intermediate A into tetrahydrofuran, stirring uniformly, adding triphosgene, heating to 50-55 ℃ for reaction for 5-6h, removing solvent in vacuum, washing, drying and purifying to obtain an intermediate B; adding the intermediate B into N, N-dimethylformamide, adding 0.5mol/L N-butylamine N, N-dimethylformamide solution under nitrogen atmosphere, stirring at room temperature for reaction for 72-80h, adding the product into cold diethyl ether for precipitation, filtering, washing and drying to obtain a corrosion inhibitor;
further, the perfluoro-group acrylic acid ester is any one of perfluoro-decyl ethyl acrylic acid ester and perfluoro-octyl ethyl acrylic acid ester;
further, the L-cysteine: the mass ratio of the perfluoro acrylic ester is 2.7 (3.7-4.2); the intermediate A: the mass ratio of triphosgene is (3.2-4) (0.6-0.7).
Further, the polyvinylpyrrolidone: styrene: the mass ratio of the potassium persulfate is (1-2), and the weight ratio of the potassium persulfate is (5-10), and is 0.2; the polystyrene solution: ammonium hydroxide: the mass ratio of the tetraethoxysilane is 1:0.8 (0.9-1); the concentration of the acetone solution of the 2-mercaptobenzothiazole is 20-30mg/mL; the addition amount of the modified nano silicon dioxide nanospheres is 1-3wt% of the mass of the epoxy resin.
Further, the furanyl benzoxazine modified siloxane: the molar ratio of the maleimide modified siloxane is (2-3): 1.
Further, the graphene oxide: hydrazine hydrate: the mass ratio of the corrosion inhibitor microcapsules is 1:1 (1-3); the addition amount of the modified reduced graphene oxide is 0.5-0.8wt% of the mass of the polytetrafluoroethylene resin.
Further, the spraying thickness of the coating A is 80-100 mu m, the spraying thickness of the coating B is 20-30 mu m, and the spraying thickness of the coating C is 55-65 mu m.
Further, the specific surface pretreatment step is to remove oil and alkali wash the surface of the aluminum alloy template;
Further, the sand mould used for sand blasting is 120# iron sand, and the sand blasting pressure is 3kg;
Further, the specification of the polishing groove liquid used in the chemical polishing is 20g/L aluminum ion concentration, 80% phosphoric acid and 20% sulfuric acid; the temperature is 85 ℃; the chemical polishing time is 60s;
Further, the specification of the oxidation tank liquor used for the anodic oxidation is 200g/L sulfuric acid concentration and 8g/L aluminum ion concentration; the temperature is 25 ℃; the voltage is 12V; the anodic oxidation time was 20min.
Compared with the prior art, the invention has the following beneficial effects:
According to the invention, the mesoporous silica nano-microsphere is prepared by taking polystyrene particles as a solid template, then the prepared mesoporous silica nano-microsphere is taken as a container, 2-mercaptobenzothiazole is loaded on the mesoporous silica nano-microsphere to prepare the modified silica nano-microsphere, the modified silica nano-microsphere is added into epoxy resin and uniformly stirred to serve as a sealing agent for anodic oxidation of an aluminum alloy template, and the modified silica nano-microsphere is added on the surface of an anodic oxide film in a spraying manner, so that on one hand, the defect structure on the anodic oxide film can be filled up, and on the other hand, the wear resistance of a coating formed by a coating A is greatly improved by adding the modified silica nano-microsphere as a reinforcing filler; if the traditional empty mesoporous silica nanoparticle is used as a filler, and the 2-mercaptobenzothiazole which is lack of load is used as a lubricant, so that the filler is unevenly dispersed in the coating, the irregularity of the surface of the coating is increased, the number of interlocking points of sliding abrasion between friction surfaces in the friction process is increased, the friction coefficient is increased, the wear resistance of the coating is reduced, and the defect structure on an anodic oxide film cannot be filled completely. When the sliding abrasion load is applied, the mesoporous silica nano microsphere in the coating A plays a role of self-lubrication similar to a rolling bearing during friction due to the spherical structure of the mesoporous silica nano microsphere, the abrasion of the coating is reduced, and meanwhile, the loaded 2-mercaptobenzothiazole is released to the abrasion surface to further lubricate the two abrasion surfaces, so that the friction coefficient of the coating is greatly reduced, and the abrasion resistance of the coating is improved.
In order to further enhance the corrosion resistance of the aluminum alloy template, polytetrafluoroethylene is used as matrix resin of the coating C, polypyrrole microcapsules containing self-made corrosion inhibitors are loaded on reduced graphene oxide, and polytetrafluoroethylene is added for uniform mixing, so that the coating C with the corrosion resistance is prepared; the addition of polypyrrole can promote the compactness of the coating, and inhibit and delay the nuclear chemical corrosion process of chemical corrosion through the protection effect on the anode and the cathode; the reduced graphene oxide can play a role of a labyrinth effect in polytetrafluoroethylene by virtue of a lamellar structure, so that the corrosion path of a corrosion medium is prolonged; the paint A and the paint B of the middle layer effectively isolate the 'galvanic corrosion' effect generated by the direct contact of the graphene and the metal surface, and prevent the problem of the acceleration loss of the metal serving as an anode; when the corrosion inhibitor is corroded by an acidic medium, the corrosion inhibitor in the polypyrrole microcapsule is released, and poly-L-cysteine with a side chain grafted with perfluorooctyl ethyl acrylate is used as the corrosion inhibitor, and the poly-L-cysteine with a hydrophobic and low-surface property in the structure is continuously migrated to the surface of the coating with the help of a fluorine-containing chain segment, so that a passivation film is formed on the outermost layer, and the corrosion of the corrosive medium can be effectively prevented; when the polypyrrole is corroded by alkaline medium, polypyrrole plays a role in delaying corrosion preferentially, simultaneously stimulates metal ion enrichment, induces the release of a corrosion inhibitor in the polypyrrole microcapsule, and blocks the corrosion of the corrosion medium; the mutual synergistic effect between the substances greatly improves the corrosion resistance of the coating formed by spraying the coating C. The polypyrrole microcapsule-loaded corrosion inhibitor not only can provide excellent corrosion resistance in the complete state of the coating, but also can perform self-repairing function on the damaged coating due to pH change after the damage to stimulate the release of the corrosion inhibitor when the coating is damaged, and further improves the corrosion resistance of the coating formed by spraying the coating C; meanwhile, as the side chain of the corrosion inhibitor is grafted with the perfluorooctyl ethyl acrylate, the dispersion performance of the modified reduced graphene oxide in polytetrafluoroethylene can be improved.
In order to endow the aluminum alloy template with excellent wear resistance and corrosion resistance, the coating A is used as a hard layer, and the coating C is used as a soft layer to be compounded together; firstly, utilizing the sliding effect of the graphene sheet layer in the coating C and the soft buffering effect of polytetrafluoroethylene, when the aluminum alloy template is stressed, the elastic deformation generated by the soft layer preferentially buffers part of stress, and the force applied to the metal matrix is reduced; the rigidity of the hard layer cured by the modified silica nano-microspheres and the epoxy resin in the coating A is utilized to provide enough supporting force for the sprayed coating of the upper coating C, and the abrasion resistance of the aluminum alloy template is further improved by the synergy of the hardness and the softness between the two coatings; however, due to the self-properties of polytetrafluoroethylene, after the coating C is directly sprayed on the coating formed by the coating A for curing, the coating formed by the coating C has low adhesive force and low bonding strength with the coating formed by the coating A, so that the coating is easy to fall off; the surface tension of the common traditional adhesive is far higher than the critical surface tension of the polytetrafluoroethylene surface, so that the traditional adhesive cannot be wetted on the polytetrafluoroethylene surface, and effective bonding cannot be realized.
In order to solve the problem of coating shedding, the invention takes aminopropyl end-capped polydimethylsiloxane with the surface energy similar to that of polytetrafluoroethylene as a main chain segment in the molecular structure of the coating B to respectively prepare a coating C which contains furyl benzoxazine modified siloxane and maleimide modified siloxane and is blended as a binder of the coating A and the coating C; on one hand, by utilizing the characteristic that the surface tension of polysiloxane is similar to that of polytetrafluoroethylene, the coating B can be rapidly spread and infiltrated on the surface of polytetrafluoroethylene resin; on the other hand, in order to reduce the polarity of the coating B and improve the adhesive property of the coating B as much as possible (fluorine atoms are easy to form hydrogen bonds with hydroxyl groups to realize adhesion, but a large amount of hydrogen bonds are introduced into the coating B to cause polarity increase, and high-polarity substances are difficult to spread and wet on the surface of polytetrafluoroethylene), the invention selects to introduce benzoxazine groups into siloxane, so that the problems of polarity increase, spreading and infiltration capability reduction of the coating B caused by exposure of phenolic hydroxyl groups can be avoided; when benzoxazine is heated for ring-opening polymerization, a large number of phenolic hydroxyl groups are generated, the phenolic hydroxyl groups can form hydrogen bonds with higher strength with fluorine atoms, and effective bonding is realized under the help of a large number of phenolic hydroxyl groups serving as hydrogen bond action sites, so that the bonding performance of the coating B is improved while the polarity of the coating B is reduced as much as possible. The furan groups and the maleimide groups on the two modified siloxanes in the coating B can generate Diels-Alder reaction at a temperature lower than the polymerization ring opening temperature of benzoxazine, a stable and flat adhesive layer is formed on the surface of the coating A, the uniformity of the adhesive strength of each position between the coating C and the coating is ensured, and the adhesive tightness degree between the coatings A, B, C is greatly improved.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the following examples, polyvinylpyrrolidone specification: molecular weight 10000, available from Shanghai Ala Biochemical technologies Co., ltd; the molecular weight of the bisaminopropyl-terminated polydimethylsiloxane was 1000, available from Shanghai Ala Biochemical technologies Co., ltd; graphene oxide was purchased from Shanghai Ala Biochemical technologies Co., ltd; the rest raw materials are all sold in the market.
The preparation method of the silica nanospheres comprises the following steps of
Adding 1g of polyvinylpyrrolidone into deionized water, uniformly stirring, adding 5g of styrene and 0.2g of potassium persulfate, and heating to 70 ℃ for reaction for 24 hours to obtain a polystyrene solution; adding 1g of polystyrene solution into 50mL of ethanol, uniformly stirring, adding 0.8g of ammonium hydroxide and 1g of tetraethoxysilane, stirring at room temperature for reaction for 18h, centrifuging, filtering, washing, drying at room temperature, and performing heat treatment at 500 ℃ for 5h to obtain the silica nanospheres.
The specific steps of the surface pretreatment are to remove oil and alkali wash the surface of the aluminum alloy template;
the sand mould used for sand blasting is 120# iron sand, and the sand blasting pressure is 3kg;
the specification of the polishing groove liquid used in the chemical polishing is 20g/L aluminum ion concentration, 80% phosphoric acid and 20% sulfuric acid; the temperature is 85 ℃; the chemical polishing time is 60s;
The specification of the oxidation tank liquor used for the anodic oxidation is 200g/L sulfuric acid concentration and 8g/L aluminum ion concentration; the temperature is 25 ℃; the voltage is 12V; the anodic oxidation time was 20min.
Example 1: a surface treatment process of a high-strength wear-resistant aluminum alloy template comprises the following steps: s1: adding 1g of silica nanospheres into 20mg/mL of 2-mercaptobenzothiazole acetone solution, stirring at room temperature for reaction for 36h, centrifuging, washing, and drying at 60 ℃ to obtain modified silica nanospheres; adding 1g of modified nano silicon dioxide nanospheres into 100g of epoxy resin, and uniformly stirring to obtain a coating A;
S2: adding 1mmol of double aminopropyl end-capped polydimethylsiloxane into tetrahydrofuran, uniformly stirring, adding 4 mmoles of 13.16mol/L formaldehyde solution under the conditions of nitrogen atmosphere and ice bath, stirring for 1h, adding 2mmol of catechol, heating to reflux for 5h, performing rotary evaporation, extracting, washing and drying to obtain phenolic hydroxyl benzoxazine modified siloxane; adding 3.3g of paraformaldehyde into 100mL of deionized water, regulating the pH to 8.5, heating to reflux, stirring until the paraformaldehyde is completely dissolved, cooling to room temperature, adding 4.85g of furfuryl amine and 20mL of dioxane, stirring at room temperature for 1h, adding 3.9g of phenolic hydroxyl benzoxazine modified siloxane, heating to stirring, refluxing for 5h, extracting, washing and extracting to obtain furyl benzoxazine modified siloxane; adding 1mmol of aminopropyl end-capped polydimethylsiloxane and 8mmol of maleic anhydride into glacial acetic acid, stirring for 2 hours at room temperature, heating to 140 ℃ for reaction for 6 hours, cooling, adding dichloromethane, standing, washing, drying, and removing a solvent to obtain maleimide modified siloxane; heating 3mmol of furyl benzoxazine modified siloxane and 1mmol of maleimide modified siloxane to 45 ℃ and uniformly mixing, then adding the mixture into N, N-dimethylformamide, uniformly stirring, and performing rotary evaporation to obtain a coating B;
s3: adding 2.7g of L-cysteine into 100mL of deionized water, uniformly stirring, adjusting the pH to 7.3, adding 3.7g of perfluorooctyl ethyl acrylic acid vinegar, stirring at room temperature for reaction for 16h, adding ethanol for precipitation, washing, filtering and drying to obtain an intermediate A; adding 3.2g of the intermediate A into 50mL of tetrahydrofuran, uniformly stirring, adding 0.6g of triphosgene, heating to 50 ℃ for reaction for 5h, removing the solvent in vacuum, washing, drying and purifying to obtain an intermediate B; adding 0.77g of intermediate B into N, N-dimethylformamide, adding 150 mu L of 0.5mol/L of N-butylamine N, N-dimethylformamide solution under nitrogen atmosphere, stirring at room temperature for reaction for 72 hours, adding the product into cold diethyl ether for precipitation, filtering, washing and drying to obtain a corrosion inhibitor; adding 1g of corrosion inhibitor and 500mg of methyl orange into deionized water, stirring for 5 hours at room temperature, adding 6g of ferric trichloride hexahydrate, stirring for 1 hour at room temperature, adding 2g of pyrrole, adjusting the pH to 8, stirring for 24 hours at room temperature, filtering, washing and drying to obtain a corrosion inhibitor microcapsule; adding 1g of graphene oxide into deionized water, performing ultrasonic dispersion for 2 hours to form 1mg/mL graphene oxide dispersion liquid, adjusting pH to 9, adding 1g of hydrazine hydrate, heating to 90-95 ℃ for reaction for 1-2 hours, adding 1g of corrosion inhibitor microcapsule, heating to reflux for reaction for 4 hours, washing, and removing unreacted substances to obtain modified reduced graphene oxide; ultrasonically dispersing 0.5g of modified reduced graphene oxide in 100g of polytetrafluoroethylene resin to obtain a coating C;
S4: sequentially carrying out polishing pretreatment, sand blasting, chemical polishing, anodic oxidation, heating the spraying coating A to 90 ℃ for curing for 1.5h, heating the spraying coating B to 60 ℃ for pre-curing for 2.5h, and respectively curing the spraying coating C at 100 ℃, 110 ℃ and 120 ℃ for 2h to obtain a high-strength wear-resistant aluminum alloy template;
The spray thickness of the paint A was 80 μm, the spray thickness of the paint B was 20 μm, and the spray thickness of the paint C was 55 μm.
Example 2: a surface treatment process of a high-strength wear-resistant aluminum alloy template comprises the following steps: s1: adding 1g of silica nanospheres into 20mg/mL of 2-mercaptobenzothiazole acetone solution, stirring at room temperature for reaction for 36h, centrifuging, washing, and drying at 60 ℃ to obtain modified silica nanospheres; adding 2g of modified nano silicon dioxide nanospheres into 100g of epoxy resin, and uniformly stirring to obtain a coating A;
S2: adding 1mmol of double aminopropyl end-capped polydimethylsiloxane into tetrahydrofuran, uniformly stirring, adding 4 mmoles of 13.16mol/L formaldehyde solution under the conditions of nitrogen atmosphere and ice bath, stirring for 1h, adding 2mmol of catechol, heating to reflux for 5h, performing rotary evaporation, extracting, washing and drying to obtain phenolic hydroxyl benzoxazine modified siloxane; adding 3.3g of paraformaldehyde into 100mL of deionized water, regulating the pH to 8.5, heating to reflux, stirring until the paraformaldehyde is completely dissolved, cooling to room temperature, adding 4.85g of furfuryl amine and 20mL of dioxane, stirring at room temperature for 1h, adding 3.9g of phenolic hydroxyl benzoxazine modified siloxane, heating to stirring, refluxing for 5h, extracting, washing and extracting to obtain furyl benzoxazine modified siloxane; adding 1mmol of aminopropyl end-capped polydimethylsiloxane and 8mmol of maleic anhydride into glacial acetic acid, stirring for 2 hours at room temperature, heating to 140 ℃ for reaction for 6 hours, cooling, adding dichloromethane, standing, washing, drying, and removing a solvent to obtain maleimide modified siloxane; heating 2.5mmol of furyl benzoxazine modified siloxane and 1mmol of maleimide modified siloxane to 45 ℃ and uniformly mixing, then adding into N, N-dimethylformamide, uniformly stirring, and performing rotary evaporation to obtain a coating B;
S3: adding 2.7g of L-cysteine into 100mL of deionized water, uniformly stirring, adjusting the pH to 7.3, adding 3.7g of perfluorooctyl ethyl acrylic acid vinegar, stirring at room temperature for reaction for 16h, adding ethanol for precipitation, washing, filtering and drying to obtain an intermediate A; adding 3.2g of the intermediate A into 50mL of tetrahydrofuran, uniformly stirring, adding 0.6g of triphosgene, heating to 50 ℃ for reaction for 5h, removing the solvent in vacuum, washing, drying and purifying to obtain an intermediate B; adding 0.77g of intermediate B into N, N-dimethylformamide, adding 150 mu L of 0.5mol/L of N-butylamine N, N-dimethylformamide solution under nitrogen atmosphere, stirring at room temperature for reaction for 72 hours, adding the product into cold diethyl ether for precipitation, filtering, washing and drying to obtain a corrosion inhibitor; adding 1g of corrosion inhibitor and 500mg of methyl orange into deionized water, stirring for 5 hours at room temperature, adding 6g of ferric trichloride hexahydrate, stirring for 1 hour at room temperature, adding 2g of pyrrole, adjusting the pH to 8, stirring for 24 hours at room temperature, filtering, washing and drying to obtain a corrosion inhibitor microcapsule; adding 1g of graphene oxide into deionized water, performing ultrasonic dispersion for 2 hours to form 1mg/mL graphene oxide dispersion liquid, adjusting pH to 9, adding 1g of hydrazine hydrate, heating to 90-95 ℃ for reaction for 1-2 hours, adding 2g of corrosion inhibitor microcapsules, heating to reflux for reaction for 4 hours, washing, and removing unreacted substances to obtain modified reduced graphene oxide; ultrasonically dispersing 0.6g of modified reduced graphene oxide in 100g of polytetrafluoroethylene resin to obtain a coating C;
S4: sequentially carrying out polishing pretreatment, sand blasting, chemical polishing, anodic oxidation, heating the spraying coating A to 90 ℃ for curing for 1.5h, heating the spraying coating B to 60 ℃ for pre-curing for 2.5h, and respectively curing the spraying coating C at 100 ℃, 110 ℃ and 120 ℃ for 2h to obtain a high-strength wear-resistant aluminum alloy template;
The spray thickness of the paint A was 80 μm, the spray thickness of the paint B was 20 μm, and the spray thickness of the paint C was 55 μm.
Example 3: a surface treatment process of a high-strength wear-resistant aluminum alloy template comprises the following steps: s1: adding 1g of silica nanospheres into 20mg/mL of 2-mercaptobenzothiazole acetone solution, stirring at room temperature for reaction for 36h, centrifuging, washing, and drying at 60 ℃ to obtain modified silica nanospheres; adding 3g of modified nano silicon dioxide nanospheres into 100g of epoxy resin, and uniformly stirring to obtain a coating A;
S2: adding 1mmol of double aminopropyl end-capped polydimethylsiloxane into tetrahydrofuran, uniformly stirring, adding 4 mmoles of 13.16mol/L formaldehyde solution under the conditions of nitrogen atmosphere and ice bath, stirring for 1h, adding 2mmol of catechol, heating to reflux for 5h, performing rotary evaporation, extracting, washing and drying to obtain phenolic hydroxyl benzoxazine modified siloxane; adding 3.3g of paraformaldehyde into 100mL of deionized water, regulating the pH to 8.5, heating to reflux, stirring until the paraformaldehyde is completely dissolved, cooling to room temperature, adding 4.85g of furfuryl amine and 20mL of dioxane, stirring at room temperature for 1h, adding 3.9g of phenolic hydroxyl benzoxazine modified siloxane, heating to stirring, refluxing for 5h, extracting, washing and extracting to obtain furyl benzoxazine modified siloxane; adding 1mmol of aminopropyl end-capped polydimethylsiloxane and 8mmol of maleic anhydride into glacial acetic acid, stirring for 2 hours at room temperature, heating to 140 ℃ for reaction for 6 hours, cooling, adding dichloromethane, standing, washing, drying, and removing a solvent to obtain maleimide modified siloxane; heating 2mmol of furyl benzoxazine modified siloxane and 1mmol of maleimide modified siloxane to 45 ℃ and uniformly mixing, then adding the mixture into N, N-dimethylformamide, uniformly stirring, and performing rotary evaporation to obtain a coating B;
S3: adding 2.7g of L-cysteine into 100mL of deionized water, uniformly stirring, adjusting the pH to 7.3, adding 3.7g of perfluorooctyl ethyl acrylic acid vinegar, stirring at room temperature for reaction for 16h, adding ethanol for precipitation, washing, filtering and drying to obtain an intermediate A; adding 3.2g of the intermediate A into 50mL of tetrahydrofuran, uniformly stirring, adding 0.6g of triphosgene, heating to 50 ℃ for reaction for 5h, removing the solvent in vacuum, washing, drying and purifying to obtain an intermediate B; adding 0.77g of intermediate B into N, N-dimethylformamide, adding 150 mu L of 0.5mol/L of N-butylamine N, N-dimethylformamide solution under nitrogen atmosphere, stirring at room temperature for reaction for 72 hours, adding the product into cold diethyl ether for precipitation, filtering, washing and drying to obtain a corrosion inhibitor; adding 1g of corrosion inhibitor and 500mg of methyl orange into deionized water, stirring for 5 hours at room temperature, adding 6g of ferric trichloride hexahydrate, stirring for 1 hour at room temperature, adding 2g of pyrrole, adjusting the pH to 8, stirring for 24 hours at room temperature, filtering, washing and drying to obtain a corrosion inhibitor microcapsule; adding 1g of graphene oxide into deionized water, performing ultrasonic dispersion for 2 hours to form 1mg/mL graphene oxide dispersion liquid, adjusting pH to 9, adding 1g of hydrazine hydrate, heating to 90-95 ℃ for reaction for 1-2 hours, adding 3g of corrosion inhibitor microcapsules, heating to reflux for reaction for 4 hours, washing, and removing unreacted substances to obtain modified reduced graphene oxide; ultrasonically dispersing 0.8g of modified reduced graphene oxide in 100g of polytetrafluoroethylene resin to obtain a coating C;
S4: sequentially carrying out polishing pretreatment, sand blasting, chemical polishing, anodic oxidation, heating the spraying coating A to 90 ℃ for curing for 1.5h, heating the spraying coating B to 60 ℃ for pre-curing for 2.5h, and respectively curing the spraying coating C at 100 ℃, 110 ℃ and 120 ℃ for 2h to obtain a high-strength wear-resistant aluminum alloy template;
The spray thickness of the paint A was 80 μm, the spray thickness of the paint B was 20 μm, and the spray thickness of the paint C was 55 μm.
Comparative example 1: paint B was prepared using a commercially available phenolic glue with example 1 and tested for adhesion by pulling, see the test section for details.
Comparative example 2: a surface treatment process of a high-strength wear-resistant aluminum alloy template comprises the following steps: s1: adding 1g of silica nanospheres into 20mg/mL of 2-mercaptobenzothiazole acetone solution, stirring at room temperature for reaction for 36h, centrifuging, washing, and drying at 60 ℃ to obtain modified silica nanospheres; adding 1g of modified nano silicon dioxide nanospheres into 100g of epoxy resin, and uniformly stirring to obtain a coating A;
S2: adding 1mmol of double aminopropyl end-capped polydimethylsiloxane into tetrahydrofuran, uniformly stirring, adding 4 mmoles of 13.16mol/L formaldehyde solution under the conditions of nitrogen atmosphere and ice bath, stirring for 1h, adding 2mmol of catechol, heating to reflux for 5h, performing rotary evaporation, extracting, washing and drying to obtain phenolic hydroxyl benzoxazine modified siloxane; adding the phenolic hydroxyl benzoxazine modified siloxane into N, N-dimethylformamide, uniformly stirring, and performing rotary evaporation to obtain a coating B;
s3: adding 2.7g of L-cysteine into 100mL of deionized water, uniformly stirring, adjusting the pH to 7.3, adding 3.7g of perfluorooctyl ethyl acrylic acid vinegar, stirring at room temperature for reaction for 16h, adding ethanol for precipitation, washing, filtering and drying to obtain an intermediate A; adding 3.2g of the intermediate A into 50mL of tetrahydrofuran, uniformly stirring, adding 0.6g of triphosgene, heating to 50 ℃ for reaction for 5h, removing the solvent in vacuum, washing, drying and purifying to obtain an intermediate B; adding 0.77g of intermediate B into N, N-dimethylformamide, adding 150 mu L of 0.5mol/L of N-butylamine N, N-dimethylformamide solution under nitrogen atmosphere, stirring at room temperature for reaction for 72 hours, adding the product into cold diethyl ether for precipitation, filtering, washing and drying to obtain a corrosion inhibitor; adding 1g of corrosion inhibitor and 500mg of methyl orange into deionized water, stirring for 5 hours at room temperature, adding 6g of ferric trichloride hexahydrate, stirring for 1 hour at room temperature, adding 2g of pyrrole, adjusting the pH to 8, stirring for 24 hours at room temperature, filtering, washing and drying to obtain a corrosion inhibitor microcapsule; adding 1g of graphene oxide into deionized water, performing ultrasonic dispersion for 2 hours to form 1mg/mL graphene oxide dispersion liquid, adjusting pH to 9, adding 1g of hydrazine hydrate, heating to 90-95 ℃ for reaction for 1-2 hours, adding 1g of corrosion inhibitor microcapsule, heating to reflux for reaction for 4 hours, washing, and removing unreacted substances to obtain modified reduced graphene oxide; ultrasonically dispersing 0.5g of modified reduced graphene oxide in 100g of polytetrafluoroethylene resin to obtain a coating C;
S4: sequentially carrying out polishing pretreatment, sand blasting, chemical polishing, anodic oxidation, heating the spraying coating A to 90 ℃ for curing for 1.5h, heating the spraying coating B to 60 ℃ for pre-curing for 2.5h, and respectively curing the spraying coating C at 100 ℃, 110 ℃ and 120 ℃ for 2h to obtain a high-strength wear-resistant aluminum alloy template;
The spray thickness of the paint A was 80 μm, the spray thickness of the paint B was 20 μm, and the spray thickness of the paint C was 55 μm.
Comparative example 3: a surface treatment process of a high-strength wear-resistant aluminum alloy template comprises the following steps: s1: adding 1g of mesoporous nano silicon dioxide nanospheres into 100g of epoxy resin, and uniformly stirring to obtain a coating A;
The remaining steps were the same as in example 1.
Comparative example 4: a surface treatment process of a high-strength wear-resistant aluminum alloy template comprises the following steps:
s3: ultrasonically dispersing 0.5g of graphene oxide in 100g of polytetrafluoroethylene resin to obtain a coating C;
The remaining steps were the same as in example 1.
And (3) testing: abrasion resistance test: a steel ball bearing with a diameter of 4mm was placed on the surface of the aluminum alloy template coating prepared in examples 1 to 3 and comparative examples 2 to 4, a force of 5N was applied in the vertical direction, and the coating wear rate was measured by rubbing back and forth 6000 times at a speed of 0.05 m/s.
Corrosion resistance test: according to GB/T1771-2007 test of corrosion resistance of an aluminum alloy template, a cross scratch is scored on the surface of the aluminum alloy template, the aluminum alloy template is subjected to edge sealing treatment by paraffin and rosin, the salt spray test condition is 35 ℃, the salt water concentration is 5wt%, and the time is 720h.
Self-repairing performance test: firstly, testing initial gloss of the surface of an aluminum alloy template coating in examples 1-3 and comparative examples 2-4, namely, G 0, rubbing the surface of the coating for 30 times in a transverse and vertical manner by using steel wool, cleaning the surface, testing damaged gloss G 1, standing for 24 hours, measuring the gloss G 2 of the repaired coating, and calculating self-repairing efficiency eta; performing a single test on the coating in the embodiment 1, after cleaning the damaged surface, heating the aluminum alloy template at 120 ℃ for 30min, standing for 24, measuring the glossiness of the repaired coating, and calculating the self-repairing efficiency eta 1;
η＝(G2-G1)/(G0-G1)×100％。
adhesion test: the pullout heads were adhered to the surfaces of the polytetrafluoroethylene coatings C of example 1 using commercially available phenolic glue and coating B, respectively, and the adhesion was tested by the pullout method.
Table I aluminum alloy template Performance test data
Table two example 1 self-healing efficiency comparative data
| Example 1 | |
| Self-healing efficiency eta/% | 77.76 |
| Self-healing efficiency η 1/% | 83.22 |
Conclusion: the aluminum alloy templates prepared in the examples 1-3 have excellent wear resistance and corrosion resistance.
Comparative example 1 uses a commercially available adhesive phenolic glue with poor adhesion to polytetrafluoroethylene.
Comparative example 2 phenolic hydroxyl benzoxazine modified siloxane was used as coating B, and due to the lack of low temperature Diels-Alder reaction of phenolic hydroxyl groups, the spreading and wetting properties of coating B were reduced, the coating dispersibility of coating B was reduced, the adhesive strength was reduced, the surface flatness of the coating was reduced, resulting in improved coating wear rate and reduced self-healing efficiency.
Comparative example 3 using ordinary mesoporous silica nanoparticle (partially self-made in the present examples) instead of modified silica nanoparticle in coating a resulted in reduced dispersion properties, reduced coating surface flatness, increased coating wear rate, and reduced self-healing efficiency.
Comparative example 4 the modified reduced graphene oxide in coating C was replaced with ordinary graphene oxide, resulting in loss of the self-healing properties of the coating and a decrease in corrosion resistance.
Due to the thermal reversibility of the coating B, diels-Alder reaction can be realized at 120 ℃, so that the coating B is promoted to be quickly repaired, and the self-repairing efficiency of the whole coating is improved.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. A surface treatment process of a high-strength wear-resistant aluminum alloy template is characterized by comprising the following steps of: the method comprises the following steps:
S1: adding polyvinylpyrrolidone into deionized water, stirring uniformly, adding styrene and potassium persulfate, heating to 70-75 ℃ and reacting for 24-26h to obtain polystyrene solution; adding polystyrene solution into ethanol, stirring uniformly, adding ammonium hydroxide and tetraethoxysilane, stirring at room temperature for reaction for 18-20h, centrifuging, filtering, washing, drying at room temperature, and performing heat treatment at 500-550 ℃ for 5-6h to obtain silica nanospheres; adding the silica nanospheres into an acetone solution of 2-mercaptobenzothiazole, stirring at room temperature for reaction for 36-40h, centrifuging, washing, and drying at 60-65 ℃ to obtain modified silica nanospheres; adding the modified nano silicon dioxide nanospheres into epoxy resin, and uniformly stirring to obtain a coating A;
s2: heating furyl benzoxazine modified siloxane and maleimide modified siloxane to 45-50 ℃, uniformly mixing, adding the mixture into N, N-dimethylformamide, uniformly stirring, and performing rotary evaporation to obtain a coating B;
S3: adding graphene oxide into deionized water, performing ultrasonic dispersion for 2-2.5h, adjusting the pH to 9-10, adding hydrazine hydrate, heating to 90-95 ℃ for reaction for 1-2h, adding a corrosion inhibitor microcapsule, heating to reflux for reaction for 4-6h, washing, and removing unreacted substances to obtain modified reduced graphene oxide; ultrasonically dispersing modified reduced graphene oxide in polytetrafluoroethylene resin to obtain a coating C;
S4: sequentially carrying out polishing pretreatment, sand blasting, chemical polishing, anodic oxidation, heating the spray coating A to 90-95 ℃ for curing for 1.5-2h, heating the spray coating B to 60-65 ℃ for pre-curing for 2-3h, and respectively curing the spray coating C at 100 ℃, 110 ℃ and 120 ℃ for 2h to obtain a high-strength wear-resistant aluminum alloy template;
the preparation method of the furyl benzoxazine modified siloxane comprises the following steps:
adding the diaminopropyl end-capped polydimethylsiloxane into tetrahydrofuran, uniformly stirring, adding 13.16mol/L-14.23mol/L formaldehyde solution under the conditions of nitrogen atmosphere and ice bath, stirring for 1-1.5h, adding catechol, heating to reflux reaction for 5-6h, performing rotary evaporation, extracting, washing and drying to obtain phenolic hydroxyl benzoxazine modified siloxane; adding paraformaldehyde into deionized water, adjusting pH to 8-9, heating to reflux and stirring until the paraformaldehyde is completely dissolved, cooling to room temperature, adding furfuryl amine and dioxane, stirring at room temperature for 1-1.5h, adding phenolic hydroxy benzoxazine modified siloxane, heating to reflux and stirring for 5-6h, extracting, washing and extracting to obtain furyl benzoxazine modified siloxane;
The bis-aminopropyl terminated polydimethylsiloxane: formaldehyde solution: the mol ratio of catechol is 1:4 (2-3); the paraformaldehyde: furfuryl amine: the mass ratio of the phenolic hydroxyl benzoxazine modified siloxane is 3.3 (4.85-5) to 3.9;
the preparation method of the corrosion inhibitor microcapsule comprises the following steps:
Adding a corrosion inhibitor and methyl orange into deionized water, stirring for 5-6h at room temperature, adding ferric trichloride hexahydrate, stirring for 1-1.5h at room temperature, adding pyrrole, adjusting the pH to 8-9, stirring for 24-26h at room temperature, carrying out suction filtration, washing and drying to obtain a corrosion inhibitor microcapsule;
the corrosion inhibitor comprises: ferric trichloride hexahydrate: the mass ratio of the pyrrole is 1 (6-9): 2;
the preparation method of the corrosion inhibitor comprises the following steps:
adding L-cysteine into deionized water, stirring uniformly, regulating the pH to 7.3-7.5, adding perfluoro-acrylic ester, stirring at room temperature for reaction for 16-20h, adding ethanol for precipitation, washing, filtering and drying to obtain an intermediate A; adding the intermediate A into tetrahydrofuran, stirring uniformly, adding triphosgene, heating to 50-55 ℃ for reaction for 5-6h, removing solvent in vacuum, washing, drying and purifying to obtain an intermediate B; adding the intermediate B into N, N-dimethylformamide, adding 0.5mol/L N-butylamine N, N-dimethylformamide solution under nitrogen atmosphere, stirring at room temperature for reaction for 72-80h, adding the product into cold diethyl ether for precipitation, filtering, washing and drying to obtain a corrosion inhibitor;
The perfluoro acrylic ester is any one of perfluoro decyl ethyl acrylic ester or perfluoro octyl ethyl acrylic ester;
The L-cysteine: the mass ratio of the perfluoro acrylic ester is 2.7 (3.7-4.2); the intermediate A: the mass ratio of triphosgene is (3.2-4) (0.6-0.7).
2. The surface treatment process of the high-strength wear-resistant aluminum alloy template according to claim 1, wherein the surface treatment process comprises the following steps of: the preparation method of the maleimide modified siloxane comprises the following steps:
Adding aminopropyl end-capped polydimethylsiloxane and maleic anhydride into glacial acetic acid, stirring for 2-2.5h at room temperature, heating to 140-145 ℃ for reaction for 6-6.5h, cooling, adding dichloromethane, standing, washing, drying, and removing solvent to obtain maleimide modified siloxane;
The aminopropyl terminated polydimethylsiloxane: the molar ratio of maleic anhydride is 1 (8-9).
3. The surface treatment process of the high-strength wear-resistant aluminum alloy template according to claim 1, wherein the surface treatment process comprises the following steps of: in step S1, the polyvinylpyrrolidone: styrene: the mass ratio of the potassium persulfate is (1-2), and the weight ratio of the potassium persulfate is (5-10), and is 0.2; the polystyrene solution: ammonium hydroxide: the mass ratio of the tetraethoxysilane is 1:0.8 (0.9-1); the concentration of the acetone solution of the 2-mercaptobenzothiazole is 20-30mg/mL; the addition amount of the modified nano silicon dioxide nanospheres is 1-3wt% of the mass of the epoxy resin.
4. The surface treatment process of the high-strength wear-resistant aluminum alloy template according to claim 1, wherein the surface treatment process comprises the following steps of: in step S2, the furanyl benzoxazine-modified siloxane: the molar ratio of the maleimide modified siloxane is (2-3): 1.
5. The surface treatment process of the high-strength wear-resistant aluminum alloy template according to claim 1, wherein the surface treatment process comprises the following steps of: in step S3, the graphene oxide: hydrazine hydrate: the mass ratio of the corrosion inhibitor microcapsules is 1:1 (1-3); the addition amount of the modified reduced graphene oxide is 0.5-0.8wt% of the mass of the polytetrafluoroethylene resin.
6. The surface treatment process of the high-strength wear-resistant aluminum alloy template according to claim 1, wherein the surface treatment process comprises the following steps of: the spraying thickness of the coating A is 80-100 mu m, the spraying thickness of the coating B is 20-30 mu m, and the spraying thickness of the coating C is 55-65 mu m.
7. A high strength and wear resistant aluminum alloy template prepared by a surface treatment process of the high strength and wear resistant aluminum alloy template according to any one of claims 1 to 6.
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