CN115403993B - Water-based paint composition - Google Patents
Water-based paint composition Download PDFInfo
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- CN115403993B CN115403993B CN202211106373.8A CN202211106373A CN115403993B CN 115403993 B CN115403993 B CN 115403993B CN 202211106373 A CN202211106373 A CN 202211106373A CN 115403993 B CN115403993 B CN 115403993B
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 143
- 239000003973 paint Substances 0.000 title claims abstract description 53
- 239000000203 mixture Substances 0.000 title claims abstract description 10
- 238000000576 coating method Methods 0.000 claims abstract description 65
- 239000011248 coating agent Substances 0.000 claims abstract description 64
- 239000008367 deionised water Substances 0.000 claims abstract description 52
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 52
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 49
- 230000003647 oxidation Effects 0.000 claims abstract description 47
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000004645 polyester resin Substances 0.000 claims abstract description 36
- 229920001225 polyester resin Polymers 0.000 claims abstract description 36
- 229920003180 amino resin Polymers 0.000 claims abstract description 23
- 239000000080 wetting agent Substances 0.000 claims abstract description 21
- 239000002131 composite material Substances 0.000 claims abstract description 20
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 20
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 19
- 239000010703 silicon Substances 0.000 claims abstract description 19
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 13
- 239000013530 defoamer Substances 0.000 claims abstract description 12
- 230000035515 penetration Effects 0.000 claims abstract description 11
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 7
- -1 butynediol penetrant Substances 0.000 claims abstract description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 106
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 63
- 229910000838 Al alloy Inorganic materials 0.000 claims description 62
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 60
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 53
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 51
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 40
- 239000003792 electrolyte Substances 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 34
- 238000001035 drying Methods 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 22
- 238000004140 cleaning Methods 0.000 claims description 21
- 235000006408 oxalic acid Nutrition 0.000 claims description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- ZCLVNIZJEKLGFA-UHFFFAOYSA-H bis(4,5-dioxo-1,3,2-dioxalumolan-2-yl) oxalate Chemical compound [Al+3].[Al+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O ZCLVNIZJEKLGFA-UHFFFAOYSA-H 0.000 claims description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims description 20
- 239000000758 substrate Substances 0.000 claims description 19
- 229920005989 resin Polymers 0.000 claims description 17
- 239000011347 resin Substances 0.000 claims description 17
- 229910001200 Ferrotitanium Inorganic materials 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 15
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 11
- 238000004381 surface treatment Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 244000137852 Petrea volubilis Species 0.000 claims description 10
- 238000007743 anodising Methods 0.000 claims description 10
- 238000005238 degreasing Methods 0.000 claims description 10
- 238000011010 flushing procedure Methods 0.000 claims description 10
- 238000005498 polishing Methods 0.000 claims description 10
- 238000010926 purge Methods 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 239000008199 coating composition Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 4
- 238000007664 blowing Methods 0.000 claims description 3
- 229920001400 block copolymer Polymers 0.000 claims description 2
- 239000003002 pH adjusting agent Substances 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 claims description 2
- 239000011148 porous material Substances 0.000 abstract description 40
- 239000000463 material Substances 0.000 abstract description 25
- 238000013329 compounding Methods 0.000 abstract description 4
- IXQWNVPHFNLUGD-UHFFFAOYSA-N iron titanium Chemical compound [Ti].[Fe] IXQWNVPHFNLUGD-UHFFFAOYSA-N 0.000 abstract description 4
- 230000001276 controlling effect Effects 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 19
- 239000006185 dispersion Substances 0.000 description 17
- 239000007788 liquid Substances 0.000 description 17
- 238000003756 stirring Methods 0.000 description 16
- 238000005303 weighing Methods 0.000 description 16
- 230000000149 penetrating effect Effects 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 10
- 230000007797 corrosion Effects 0.000 description 9
- 238000005260 corrosion Methods 0.000 description 9
- 239000010410 layer Substances 0.000 description 9
- 239000002518 antifoaming agent Substances 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 238000004806 packaging method and process Methods 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 239000010407 anodic oxide Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229920000728 polyester Polymers 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- 239000011247 coating layer Substances 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 230000008595 infiltration Effects 0.000 description 3
- 238000001764 infiltration Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000013112 stability test Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000000956 alloy Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920006334 epoxy coating Polymers 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 239000011527 polyurethane coating Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
- C25D11/08—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing inorganic acids
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
- C25D11/10—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing organic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2265—Oxides; Hydroxides of metals of iron
- C08K2003/2275—Ferroso-ferric oxide (Fe3O4)
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Paints Or Removers (AREA)
Abstract
The invention provides a water-based paint composition, which is prepared by compounding water-based saturated polyester resin, cross-linking agent amino resin, iron oxide black, composite iron titanium powder, dispersing wetting agent, water-based organic silicon defoamer, butynediol penetrant, propylene glycol penetration auxiliary agent, pH regulator and deionized water, wherein the paint can effectively enter into a conical pore canal of anodic oxidation, so that high binding force and high stability coating material are obtained.
Description
Technical Field
The invention provides a water-based coating composition, in particular to a high-binding force coating, and particularly relates to a polyester coating.
Background
With the development of scientific technology, new materials with excellent performance are continuously developed, and the material has light weight, high strength and high tolerance
The excellent properties such as corrosion and the like lead the new material to be applied to various fields including aerospace, building materials and household daily necessities. Among the new materials, the high-performance composite material is the most outstanding in performance, is an important development trend of the new material, is formed by compounding two or more materials through a certain process, has the advantages of the raw materials, and can obtain the new performance through a compounding effect. It is essentially different from the simple mixing of general materials, and retains the important characteristics of the original constituent phase.
The aqueous coating refers to a mixed system formed by dispersing a film-forming substance and a pigment filler in an aqueous medium. Two general categories can be distinguished by the state of dispersion: emulsion type and solution type. Emulsion-type means that the film-forming material in the coating is not itself
Is soluble in water but forms a resin emulsion, such as an epoxy emulsion, in water under the promotion of an emulsifier or other adjuvant. The solution type resin is acrylic resin containing carboxyl and hydroxyl, which is most representative, because the water-soluble resin contains hydrophilic groups such as carboxyl, hydroxyl and the like, the resin can be dissolved in an aqueous solution to form a stable homogeneous solution, and the rapid development of the aqueous resin promotes the aqueous coating, and mainly comprises aqueous inorganic zinc-rich coating, aqueous epoxy coating, aqueous acrylic coating and aqueous polyurethane coating.
The polyester coating has excellent comprehensive properties such as wear resistance, impact resistance, cavitation resistance, water resistance, insulation, corrosion resistance, shock absorption and the like, has no VOC pollution, is an environment-friendly metal protective coating with high protective performance, and is widely applied to various fields such as hydropower, ships, petrochemical engineering, mining machinery, bridges, hydraulic machinery and the like.
The invention mainly aims at solving the problem of bonding strength between the metal and the coating, has poor wetting property and low bonding strength when the coating is directly applied to the metal surface due to high drying speed of the coating in the prior art, is easy to fall off under various working conditions such as cavitation, scouring and impact conditions, and loses the protection function, thus limiting the application of the coating under the related working conditions.
Disclosure of Invention
Based on the technical problems in the prior art, the invention provides a water-based paint composition, which can be efficiently filled in pore channels of an anodic oxide film of aluminum alloy by properly selecting water-based paint components, so as to obtain an aluminum alloy polyester coating material with high binding force, wherein the aluminum alloy has a conical pore channel structure with wide upper part and narrow lower part, and is suitable for filling paint.
The water-based paint comprises the following raw materials in parts by weight:
35-40 parts of water-based saturated polyester resin
15-20 parts of cross-linking agent amino resin;
7-13 parts of iron oxide black;
0.4-0.8 part of composite ferrotitanium powder;
0.3-0.7 part of dispersing wetting agent;
0.2-0.35 part of water-based organic silicon defoamer;
0.3-0.5 part of butynediol penetrant;
0.2-0.4 part of propylene glycol penetration auxiliary agent;
1-1.6 parts of pH regulator;
50-65 parts of deionized water;
wherein the mass ratio of the water-based saturated polyester resin to the amino resin is 1-3.5:1;
the coating is coated on the surface of the aluminum alloy subjected to surface treatment, and the surface of the aluminum alloy is a conical porous oxide film, and the aluminum alloy is obtained by the following method
(a) Surface cleaning treatment: sequentially polishing the surface of a substrate by using 400, 800, 1200, 1500 and 2000# SiC sand paper, placing a polished aluminum alloy sample into acetone, cleaning and degreasing under ultrasonic waves, flushing by using absolute ethyl alcohol and deionized water, and blowing and drying by using nitrogen for standby;
(b) Surface anodizing: the surface anodic oxidation treatment is carried out by taking the mixed solution of phosphoric acid, oxalic acid, citric acid, aluminum oxalate and glycol as electrolyte, and the anodic oxidation treatment process comprises
(b-1) controlling the primary voltage to be three-stage voltage, wherein the first stage voltage is 35V, the duration is 120s, the second stage voltage is 29V, the duration is 120s, the third stage voltage is 23V, the duration is 120s, the temperature is 5 ℃, and after the power supply is cut off, the three-stage voltage is 10s, the three-stage voltage is put into 5% phosphoric acid solution to be soaked for 3min, and the three-stage voltage is taken out, washed by deionized water and soaked into electrolyte;
(b-2) controlling the secondary voltage to be three-stage voltage, wherein the first stage voltage is 27V, the duration is 90s, the second stage voltage is 21V, the duration is 90s, the third stage voltage is 16V, the duration is 90s, the temperature is 10 ℃, and after the power supply is cut off, the three-stage voltage is 10s and then is put into 5% phosphoric acid solution to be soaked for 4min, and the three-stage voltage is taken out, washed by deionized water and soaked into electrolyte;
(b-3) controlling the three voltages to be three-stage voltages, wherein the first stage is 18V, the duration is 60s, the second stage is 15V, the duration is 60s, the third stage is 12V, the duration is 60s, the temperature is 15 ℃, and the third stage is 10s after the power supply is cut off, the third stage is put into 5% phosphoric acid solution to be soaked for 5min, and then taken out and washed by deionized water;
wherein the concentration of phosphoric acid is 25-30g/L, the concentration of oxalic acid is 20-25g/L, the concentration of citric acid is 6-8g/L, the concentration of aluminum oxalate is 2-4/L, and the concentration of ethylene glycol is 5-7ml/L;
(c) Nitrogen purging and drying;
the binding force between the paint and the aluminum alloy substrate is 16.3-22.5Mpa.
Further, the crosslinker amino resin is selected from the group consisting of highly alkyl etherified benzomelamine resins.
Further, the dispersing wetting agent is selected from HT-100 succinate block copolymers.
Further, the pH adjuster is selected from the group consisting of glycol amines.
Further, the polyester resin includes, but is not limited to AR-618, SK9070, WP-535, etc
Further, the preparation method of the water-based paint comprises the following steps: weighing iron oxide black, composite ferrotitanium powder, a dispersing wetting agent, a penetrating aid and half of water according to mass ratio, stirring uniformly to prepare dispersion liquid for standby, weighing polyester resin, placing the polyester resin into a stirring kettle, adding a cross-linking agent amino resin curing agent, a water-based organic silicon defoaming agent, the dispersion liquid prepared by the previous steps and the other half of water, adding a pH regulator, dispersing for 10-30 minutes at 600-1000rpm, filtering and packaging to obtain the required water-based paint, wherein the water-based paint is coated on the surface of the aluminum alloy subjected to surface treatment
Further, the diameter of the conical bottom of the conical pore canal of the conical porous oxide film is 400-500nm, and the thickness of the conical porous oxide film is 2-5 mu m.
Further, the thickness of the coating film is 10-20 μm.
The application method of the water-based paint comprises the following steps:
(1) Preparing a water-based paint: weighing 7-13 parts of iron oxide black, 0.4-0.8 part of composite ferrotitanium powder, 0.3-0.7 part of dispersing wetting agent, 0.3-0.5 part of butynediol penetrating agent, 0.2-0.4 part of propylene glycol penetrating auxiliary agent and half of water according to mass ratio, stirring uniformly to prepare a dispersion liquid for standby, weighing 35-40 parts of polyester resin, placing the polyester resin into a stirring kettle, adding 15-20 parts of cross-linking agent amino resin curing agent, 0.2-0.35 part of aqueous organic silicon defoaming agent, the dispersion liquid prepared in the previous step and the other half of water, adding a pH regulator, dispersing for 10-30 minutes at the speed of 600-1000rpm, filtering and packaging to obtain the required aqueous paint;
(2) Pretreating an aluminum alloy material;
wherein the pretreatment aluminum alloy material comprises the following steps:
(a) Surface cleaning treatment: sequentially polishing the surface of a substrate by using 400, 800, 1200, 1500 and 2000# SiC sand paper, placing a polished aluminum alloy sample into acetone, cleaning and degreasing under ultrasonic waves, flushing by using absolute ethyl alcohol and deionized water, and blowing and drying by using nitrogen for standby;
(b) Surface anodizing: the surface anodic oxidation treatment is carried out by taking the mixed solution of phosphoric acid, oxalic acid, citric acid, aluminum oxalate and glycol as electrolyte, and the anodic oxidation treatment process comprises
(b-1) controlling the primary voltage to be three-stage voltage, wherein the first stage voltage is 35V, the duration is 120s, the second stage voltage is 29V, the duration is 120s, the third stage voltage is 23V, the duration is 120s, the temperature is 5 ℃, and after the power supply is cut off, the three-stage voltage is 10s, the three-stage voltage is put into 5% phosphoric acid solution to be soaked for 3min, and the three-stage voltage is taken out, washed by deionized water and soaked into electrolyte;
(b-2) controlling the secondary voltage to be three-stage voltage, wherein the first stage voltage is 27V, the duration is 90s, the second stage voltage is 21V, the duration is 90s, the third stage voltage is 16V, the duration is 90s, the temperature is 10 ℃, and after the power supply is cut off, the three-stage voltage is 10s and then is put into 5% phosphoric acid solution to be soaked for 4min, and the three-stage voltage is taken out, washed by deionized water and soaked into electrolyte;
(b-3) controlling the three voltages to be three-stage voltages, wherein the first stage is 18V, the duration is 60s, the second stage is 15V, the duration is 60s, the third stage is 12V, the duration is 60s, the temperature is 15 ℃, and the third stage is 10s after the power supply is cut off, the third stage is put into 5% phosphoric acid solution to be soaked for 5min, and then taken out and washed by deionized water;
wherein the concentration of phosphoric acid is 25-30g/L, the concentration of oxalic acid is 20-25g/L, the concentration of citric acid is 6-8g/L, the concentration of aluminum oxalate is 2-4/L, and the concentration of ethylene glycol is 5-7ml/L
(c) Nitrogen purging and drying
(3) Coating water paint; and (3) taking the aluminum alloy prepared in the step (2) as a base material, coating the water-based paint prepared in the step (1) on the surface of the aluminum alloy, drying the surface of the coating film for 0.5-1h at normal temperature, then baking for 15-20min at 150-170 ℃, and cooling, wherein the thickness of the coating film is 10-20 mu m.
The aluminum alloy polyester coating material with high binding force can be obtained through two aspects, namely, the conical pore canal with wide upper part and narrow lower part is obtained through controlling the electrolysis parameters and the composition of electrolyte; on the other hand, by selecting and matching the coating components, the coating composition with high infiltration rate to the pore canal is obtained, and the two parts are described below.
First, it is known in the art that, in order to improve the bonding strength between a metal substrate and a coating, a pretreatment means is generally used in the prior art to improve the surface roughness of the metal substrate so as to improve the bonding strength or the peeling strength of the coating, and as disclosed in CN110437708A, the use method of the anticorrosive coating is as follows: the surface of the aluminum alloy matrix is pretreated by adopting anodic oxidation, passivation or sand blasting to improve the binding force between the coating and the substrate, for example, CN106584761A is used for carrying out anodic oxidation on the roughened surface of aluminum or aluminum alloy in phosphoric acid solution to generate an oxide film, nano-scale small holes are contained in the generated oxide film, the nano-scale small holes are uniformly and densely distributed on the surface of the aluminum or aluminum alloy, the binding force between the aluminum or aluminum alloy and plastic after injection molding is large, the aluminum or aluminum alloy has high tensile strength, and the process can be clearly seen from the process, the prior art generally carries out surface anodic oxidation treatment on the aluminum alloy, and the coating and the substrate are effectively combined through the pore structure by forming a uniform pore structure on the surface, but the anodic oxidation pore has the following problems: the pore canal size is nano-scale, and the paint is difficult to permeate; (2) The pore canal is of a straight up-down structure and is not suitable for coating of paint, and based on the problems, the aluminum alloy is subjected to surface treatment, and the surface treatment mainly comprises surface cleaning treatment, anodic oxidation treatment and post-treatment, wherein the surface cleaning treatment comprises the following steps: sequentially polishing the surface of a substrate by using 400, 800, 1200, 1500 and 2000# SiC sand paper, placing a polished aluminum alloy sample in acetone, cleaning and degreasing under ultrasonic waves, then flushing by using absolute ethyl alcohol and deionized water, and drying by using nitrogen to be used, wherein the purpose is to remove natural oxide layers, greasy dirt and impurities on the surface so as to obtain a regular and clean substrate, and the regularity of a subsequent anodic oxidation pore canal is affected by the substrate.
Then surface anodizing treatment is carried out: the surface anodic oxidation treatment is carried out by taking the mixed solution of phosphoric acid, oxalic acid, citric acid, aluminum oxalate and glycol as electrolyte, the anodic oxidation treatment process comprises (b-1) controlling the primary voltage to be three-stage voltage, wherein the first stage voltage is 35V, the duration is 120s, the second stage voltage is 29V, the duration is 120s, the third stage voltage is 23V, the duration is 120s, the temperature is 5 ℃, the mixed solution is placed into 5% phosphoric acid solution for 3min after the power supply is cut off, and the mixed solution is taken out, washed by deionized water and immersed into the electrolyte;
(b-2) controlling the secondary voltage to be three-stage voltage, wherein the first stage voltage is 27V, the duration is 90s, the second stage voltage is 21V, the duration is 90s, the third stage voltage is 16V, the duration is 90s, the temperature is 10 ℃, and after the power supply is cut off, the three-stage voltage is 10s and then is put into 5% phosphoric acid solution to be soaked for 4min, and the three-stage voltage is taken out, washed by deionized water and soaked into electrolyte;
(b-3) controlling the three voltages to be three-stage voltages, wherein the first stage is 18V, the duration is 60s, the second stage is 15V, the duration is 60s, the third stage is 12V, the duration is 60s, the temperature is 15 ℃, and the third stage is 10s after the power supply is cut off, the third stage is put into 5% phosphoric acid solution to be soaked for 5min, and then taken out and washed by deionized water;
wherein the concentration of phosphoric acid is 25-30g/L, the concentration of oxalic acid is 20-25g/L, the concentration of citric acid is 6-8g/L, the concentration of aluminum oxalate is 2-4/L, and the concentration of ethylene glycol is 5-7ml/L
(c) Nitrogen purging and drying
It can be seen clearly that the anodic oxidation treatment process mainly adjusts the electrolytic parameters and the electrolyte, and aims to obtain a conical pore canal with a porous layer as a main part and an extremely thin shielding layer, wherein the conical pore canal with a wide upper part and a narrow lower part of the porous layer has a diameter size of 400-500nm and a thickness (the height of the conical pore canal) of 2-5 μm.
The electrolyte adopted by the invention is an aqueous solution of phosphoric acid, oxalic acid, citric acid, aluminum oxalate 2-4/L and glycol, the pore canal of the anodic oxide film obtained by phosphoric acid known by the person skilled in the art is larger, the pore canal of oxalic acid is more regular, citric acid is added in the pore canal to further increase the size of the anodic oxide film, the pore canal of the anodic oxide film obtained by acid treatment used in the prior art is about 20-100nm in size and smaller in size, the size is not suitable for coating and filling, the size of 150-200nm can be obtained by acid mixing pore canals, then the maximum pore canal size of 400-500nm can be achieved by subsequent phosphoric acid reaming treatment, in addition, the purpose of aluminum oxalate is to prevent the problem of membrane layer fracture caused by overhigh voltage, and the glycol is introduced to improve the regularity of the electrolyte and the exchange amount of the electrolyte.
The electrolytic parameters of the invention are three-stage depressurization treatment for multiple times, the three-stage depressurization treatment is known in the art to reduce the thickness of the shielding layer in the pore canal of the anodic oxide film, and the main effect of reducing the shielding layer by adopting three-stage depressurization is to improve the filling amount of the coating and further improve the binding force of the coating and the base material without excessive analysis.
Regarding the voltage, the first stage is at 35V for 120s, the second stage is at 29V for 120s, the third stage is at 23V for 120s, the temperature is 5 ℃, after the power is cut off, the electrolyte is soaked in 5% phosphoric acid solution for 3min, taken out, rinsed by deionized water and soaked in the electrolyte;
(b-2) controlling the secondary voltage to be three-stage voltage, wherein the first stage voltage is 27V, the duration is 90s, the second stage voltage is 21V, the duration is 90s, the third stage voltage is 16V, the duration is 90s, the temperature is 10 ℃, and after the power supply is cut off, the three-stage voltage is 10s and then is put into 5% phosphoric acid solution to be soaked for 4min, and the three-stage voltage is taken out, washed by deionized water and soaked into electrolyte;
(b-3) controlling the three voltages to be three-stage voltages, wherein the first stage is 18V, the duration is 60s, the second stage is 15V, the duration is 60s, the third stage is 12V, the duration is 60s, the temperature is 15 ℃, and the third stage is 10s after the power supply is cut off, the third stage is put into 5% phosphoric acid solution to be soaked for 5min, and then taken out and washed by deionized water;
the size of the anodic oxidation voltage can influence the aperture, thickness, distribution order and the like of the AAO oxidation film, along with the increase of the oxidation voltage, the growth speed of the oxidation film is increased, the aperture is increased, the thickness is increased, and the distribution order is enhanced, but the higher the oxidation voltage value is, the better, if the anodic oxidation voltage value is too high, the current density is increased sharply, so that the reaction is too severe, and serious breakdown phenomenon occurs at the edge of the oxidation film. In addition, if the anodic oxidation voltage value is too low, the current density will be too small, so that the dissolution rate of the oxide film is larger than the formation rate, and the anodic oxidation cannot be continued, so that the voltage value must be kept within a certain range during the oxidation reaction, the oxidation time will affect the thickness of the oxide film and the order of the holes, and the film thickness will increase with the increase of the oxidation time, but when the reaction proceeds to a certain extent, the dissolution and formation of the oxide film will reach a dynamic balance process, which will make the increase of the film thickness smooth until the reaction stops. The oxidation time is prolonged within a certain range, so that the order of the holes can be improved, but the hole walls are corroded by electrolyte due to the overlong oxidation time, so that the order of the holes is poor.
The three times of voltage of the invention is gradually reduced, the time is shortened, namely, the formation speed of alumina is slowed down, the acid electrolytic corrosion speed is increased, and in the process that the dissolution and the generation of an oxide film can reach dynamic balance, the tapered pore canal with wide upper part and narrow lower part is obtained, and the pore canal is highly ordered.
In addition, the reaction temperature is as follows: the oxidation reaction temperature mainly influences the dissolution rate of the oxide film, and as the reaction temperature increases, the dissolution rate of the oxide film increases, so that the film thickness becomes thinner and the oxidation rate is accelerated.
Regarding the paint, the paint composition is as follows:
35-40 parts of water-based saturated polyester resin
15-20 parts of cross-linking agent amino resin;
7-13 parts of iron oxide black;
0.4-0.8 part of composite ferrotitanium powder;
0.3-0.7 part of dispersing wetting agent;
0.2-0.35 part of water-based organic silicon defoamer;
0.3-0.5 part of butynediol penetrant;
0.2-0.4 part of propylene glycol penetration auxiliary agent;
1-1.6 parts of pH regulator;
50-65 parts of deionized water;
the polyester resin for the coating is mainly macromolecular long-chain resin formed by esterification reaction of polybasic acid and polyhydric alcohol. In the preparation of the coating, the structure of the film-forming resin needs to be considered according to the application and the protection field of the coating, and the polyester coating is no exception. In the polyester resin, molecules with lower molecular weight can plasticize a paint film, so that the mechanical property of the paint film is poor, and when the polyester resin with higher strength requirement is applied to the field, the polyester resin with higher molecular weight is selected as a film forming substance; in polyester resins, if the molecular weight is high, the water solubility and stability are insufficient, and the gel state is liable to occur, it should be avoided in selecting the resin. The polyester resins include, but are not limited to AR-618, SK9070, WP-535, and the like.
The purpose of the surfactant is to reduce the surface energy of the aluminum material, so that the paint can easily enter a pore canal, the defoamer is used for eliminating bubbles formed in the preparation process of the paint, effectively avoiding hydrogen generated in the anodic oxidation process from occupying the sites of the paint, easily causing fine seams in the curing process of the paint, reducing the bonding strength of the coating and a porous layer, and the bubbles can be generated by the reaction of acid and the aluminum material without overflowing and adsorbed on the inner wall of the pore canal to generate fine bubbles; in addition, regarding the penetrating agent and the penetrating auxiliary agent, the infiltration effect of the resin in the pore canal can be effectively improved.
Beneficial technical effects
(1) The invention prepares the water-based polyester coating by compounding water-based saturated polyester resin, cross-linking agent amino resin, iron oxide black, composite ferrotitanium powder, dispersing wetting agent, water-based organic silicon defoamer, butynediol penetrant, propylene glycol penetration auxiliary agent, pH regulator and deionized water, and the coating can effectively enter into a conical pore canal of anodic oxidation, thereby obtaining a coating material with high binding force and high stability.
(2) According to the invention, the anodic oxidation parameters and the anodic oxidation liquid are regulated, anodic oxidation pore channels are alternately corroded, and finally, tapered pore channels with larger pore channel sizes and wide top and narrow bottom are obtained, and the pore channels are structurally favorable for infiltration of coating raw materials, so that the pore channel filling quantity is improved.
Drawings
FIG. 1 an SEM image of anodic oxide film pore canal is obtained in comparative example 1 of the present invention.
FIG. 2 is an SEM image of anodized tunnel obtained in comparative example 2 of the present invention.
FIG. 3 is an SEM image of anodized tunnel obtained in comparative example 3 of the present invention.
FIG. 4 is an SEM image of anodized tunnel obtained according to example 2 of the present invention.
FIG. 5 is an SEM image of anodized tunnel obtained in example 3 of the invention.
FIG. 6 is a graph of bond strength for coatings of varying thickness according to the present invention;
FIG. 7 is a graph of the bond stability test of the present invention.
Detailed Description
Example 1
An aqueous coating composition prepared by the steps of: weighing iron oxide black, composite ferrotitanium powder, a dispersing wetting agent, a penetrating aid and half of water according to mass ratio, stirring uniformly to prepare dispersion liquid for standby, weighing polyester resin, placing the polyester resin into a stirring kettle, adding a cross-linking agent amino resin curing agent, a water-based organic silicon defoaming agent, the dispersion liquid prepared in the previous step and the other half of water, adding a pH regulator, dispersing for 25 minutes at the speed of 1000rpm, filtering, and packaging to obtain the required water-based paint, wherein the water-based paint is coated on the surface of the aluminum alloy subjected to surface treatment, and the surface of the aluminum alloy is a conical porous oxide film, and the water-based paint is obtained through the following steps:
(a) Surface cleaning treatment: sequentially polishing the surface of the substrate by using 400, 800, 1200, 1500 and 2000# SiC sand paper, placing the polished aluminum alloy sample into acetone, cleaning and degreasing under ultrasonic waves, flushing by using absolute ethyl alcohol and deionized water, and drying by using nitrogen to be used.
(b) Surface anodizing: the surface anodic oxidation treatment is carried out by taking mixed solution of phosphoric acid, oxalic acid, citric acid, aluminum oxalate and glycol as electrolyte, and the anodic oxidation treatment process comprises the following steps:
the primary voltage of (b-1) is controlled to be three-stage voltage, the first stage is 35V, the duration is 120s, the second stage is 29V, the duration is 120s, the third stage is 23V, the duration is 120s, the temperature is 5 ℃, after the power supply is cut off, the three-stage voltage is 10s, the three-stage voltage is put into 5% phosphoric acid solution for soaking for 3min, and the three-stage voltage is taken out, washed by deionized water and soaked into electrolyte.
Controlling the secondary voltage to be three-stage voltage, wherein the first stage voltage is 27V, the duration is 90s, the second stage voltage is 21V, the duration is 90s, the third stage voltage is 16V, the duration is 90s, the temperature is 10 ℃, and the second stage voltage is 10s, after the power supply is cut off, the second stage voltage is put into 5% phosphoric acid solution to be soaked for 4min, taken out, washed by deionized water and soaked into electrolyte.
And (b-3) controlling the three voltages to be three-stage voltages, wherein the first stage is 18V, the duration is 60s, the second stage is 15V, the duration is 60s, the third stage is 12V, the duration is 60s, the temperature is 15 ℃, and the third stage is 10s after the power supply is cut off, the third stage is put into 5% phosphoric acid solution to be soaked for 5min, and then taken out and washed by deionized water.
Wherein the concentration of phosphoric acid is 25g/L, the concentration of oxalic acid is 20g/L, the concentration of citric acid is 6g/L, the concentration of aluminum oxalate is 2/L, and the concentration of ethylene glycol is 5ml/L.
(c) And (5) nitrogen purging and drying.
The weight portions of the components are as follows:
35 parts of water-based saturated polyester resin;
crosslinking agent amino resin: 15 parts of highly alkyl etherified benzomelamine resin;
7 parts of iron oxide black;
0.4 part of composite ferrotitanium powder;
0.3 parts of HT-100 dispersing wetting agent;
0.2 parts of water-based organic silicon defoamer;
0.3 parts of butynediol penetrant;
0.2 parts of propylene glycol penetration auxiliary;
1 part of pH regulator;
50 parts of deionized water.
And (3) taking the aluminum alloy prepared in the step (2) as a base material, coating the water-based paint prepared in the step (1) on the surface of the aluminum alloy, drying the surface of the coating film for 0.75h at normal temperature, then baking for 17min at 160 ℃, and cooling.
Example 2
An aqueous coating composition prepared by the steps of: weighing iron oxide black, composite ferrotitanium powder, a dispersing wetting agent, a penetrating aid and half of water according to mass ratio, stirring uniformly to prepare dispersion liquid for standby, weighing polyester resin, placing the polyester resin into a stirring kettle, adding a cross-linking agent amino resin curing agent, a water-based organic silicon defoaming agent, the dispersion liquid prepared in the previous step and the other half of water, adding a pH regulator, dispersing for 25 minutes at the speed of 1000rpm, filtering, and packaging to obtain the required water-based paint, wherein the water-based paint is coated on the surface of the aluminum alloy subjected to surface treatment, and the surface of the aluminum alloy is a conical porous oxide film, and the water-based paint is obtained through the following steps:
(a) Surface cleaning treatment: sequentially polishing the surface of the substrate by using 400, 800, 1200, 1500 and 2000# SiC sand paper, placing the polished aluminum alloy sample into acetone, cleaning and degreasing under ultrasonic waves, flushing by using absolute ethyl alcohol and deionized water, and drying by using nitrogen to be used.
(b) Surface anodizing: the surface anodic oxidation treatment is carried out by taking mixed solution of phosphoric acid, oxalic acid, citric acid, aluminum oxalate and glycol as electrolyte, and the anodic oxidation treatment process comprises the following steps:
the primary voltage of (b-1) is controlled to be three-stage voltage, the first stage is 35V, the duration is 120s, the second stage is 29V, the duration is 120s, the third stage is 23V, the duration is 120s, the temperature is 5 ℃, after the power supply is cut off, the three-stage voltage is 10s, the three-stage voltage is put into 5% phosphoric acid solution for soaking for 3min, and the three-stage voltage is taken out, washed by deionized water and soaked into electrolyte.
Controlling the secondary voltage to be three-stage voltage, wherein the first stage voltage is 27V, the duration is 90s, the second stage voltage is 21V, the duration is 90s, the third stage voltage is 16V, the duration is 90s, the temperature is 10 ℃, and the second stage voltage is 10s, after the power supply is cut off, the second stage voltage is put into 5% phosphoric acid solution to be soaked for 4min, taken out, washed by deionized water and soaked into electrolyte.
And (b-3) controlling the three voltages to be three-stage voltages, wherein the first stage is 18V, the duration is 60s, the second stage is 15V, the duration is 60s, the third stage is 12V, the duration is 60s, the temperature is 15 ℃, and the third stage is 10s after the power supply is cut off, the third stage is put into 5% phosphoric acid solution to be soaked for 5min, and then taken out and washed by deionized water.
Wherein the concentration of phosphoric acid is 27.5g/L, the concentration of oxalic acid is 22.5g/L, the concentration of citric acid is 7g/L, the concentration of aluminum oxalate is 3g/L, and the concentration of ethylene glycol is 6ml/L.
(c) And (5) nitrogen purging and drying.
The weight portions of the components are as follows:
37.5 parts of water-based saturated polyester resin;
crosslinking agent amino resin: 17.5 parts of highly alkyl etherified benzomelamine resin;
10 parts of iron oxide black;
0.6 part of composite ferrotitanium powder;
0.5 part of HT-100 dispersing wetting agent;
0.26 parts of water-based organic silicon defoamer;
0.4 parts of butynediol penetrant;
0.3 parts of propylene glycol penetration auxiliary;
1.3 parts of pH regulator;
57.5 parts of deionized water.
And (3) taking the aluminum alloy prepared in the step (2) as a base material, coating the water-based paint prepared in the step (1) on the surface of the aluminum alloy, drying the surface of the coating film for 0.75h at normal temperature, then baking for 17min at 160 ℃, and cooling.
Example 3
An aqueous coating composition prepared by the steps of: weighing iron oxide black, composite ferrotitanium powder, a dispersing wetting agent, a penetrating aid and half of water according to mass ratio, stirring uniformly to prepare dispersion liquid for standby, weighing polyester resin, placing the polyester resin into a stirring kettle, adding a cross-linking agent amino resin curing agent, a water-based organic silicon defoaming agent, the dispersion liquid prepared in the previous step and the other half of water, adding a pH regulator, dispersing for 25 minutes at the speed of 1000rpm, filtering, and packaging to obtain the required water-based paint, wherein the water-based paint is coated on the surface of the aluminum alloy subjected to surface treatment, and the surface of the aluminum alloy is a conical porous oxide film, and the water-based paint is obtained through the following steps:
(a) Surface cleaning treatment: sequentially polishing the surface of the substrate by using 400, 800, 1200, 1500 and 2000# SiC sand paper, placing the polished aluminum alloy sample into acetone, cleaning and degreasing under ultrasonic waves, flushing by using absolute ethyl alcohol and deionized water, and drying by using nitrogen to be used.
(b) Surface anodizing: the surface anodic oxidation treatment is carried out by taking mixed solution of phosphoric acid, oxalic acid, citric acid, aluminum oxalate and glycol as electrolyte, and the anodic oxidation treatment process comprises the following steps:
the primary voltage of (b-1) is controlled to be three-stage voltage, the first stage is 35V, the duration is 120s, the second stage is 29V, the duration is 120s, the third stage is 23V, the duration is 120s, the temperature is 5 ℃, after the power supply is cut off, the three-stage voltage is 10s, the three-stage voltage is put into 5% phosphoric acid solution for soaking for 3min, and the three-stage voltage is taken out, washed by deionized water and soaked into electrolyte.
Controlling the secondary voltage to be three-stage voltage, wherein the first stage voltage is 27V, the duration is 90s, the second stage voltage is 21V, the duration is 90s, the third stage voltage is 16V, the duration is 90s, the temperature is 10 ℃, and the second stage voltage is 10s, after the power supply is cut off, the second stage voltage is put into 5% phosphoric acid solution to be soaked for 4min, taken out, washed by deionized water and soaked into electrolyte.
And (b-3) controlling the three voltages to be three-stage voltages, wherein the first stage is 18V, the duration is 60s, the second stage is 15V, the duration is 60s, the third stage is 12V, the duration is 60s, the temperature is 15 ℃, and the third stage is 10s after the power supply is cut off, the third stage is put into 5% phosphoric acid solution to be soaked for 5min, and then taken out and washed by deionized water.
Wherein the concentration of phosphoric acid is 30g/L, the concentration of oxalic acid is 25g/L, the concentration of citric acid is 8g/L, the concentration of aluminum oxalate is 4/L, and the concentration of ethylene glycol is 7ml/L.
(c) And (5) nitrogen purging and drying.
The weight portions of the components are as follows:
40 parts of water-based saturated polyester resin;
crosslinking agent amino resin: 20 parts of highly alkyl etherified benzomelamine resin;
13 parts of iron oxide black;
0.8 part of composite ferrotitanium powder;
0.7 parts of HT-100 dispersing wetting agent;
0.35 parts of water-based organic silicon defoamer;
0.5 part of butynediol penetrant;
0.4 parts of propylene glycol penetration aid;
1.6 parts of pH regulator;
65 parts of deionized water.
And (3) taking the aluminum alloy prepared in the step (2) as a base material, coating the water-based paint prepared in the step (1) on the surface of the aluminum alloy, drying the surface of the coating film for 0.75h at normal temperature, then baking for 17min at 160 ℃, and cooling.
Comparative example 1
A water-based paint composition is prepared by the steps of weighing iron oxide black, composite iron titanium powder, a dispersing wetting agent, a penetrating aid and half of water according to mass ratio, uniformly stirring to prepare a dispersion liquid for later use, weighing polyester resin, placing the polyester resin into a stirring kettle, adding a cross-linking agent amino resin curing agent, a water-based organic silicon defoaming agent, the dispersion liquid prepared in the previous step and the other half of water, adding a pH regulator, dispersing for 25 minutes at a speed of 1000rpm, filtering and packaging to obtain the required water-based paint, wherein the water-based paint is coated on the surface of an aluminum alloy subjected to surface treatment, and the surface of the aluminum alloy is a conical porous oxide film, and is obtained by the following steps:
(a) Surface cleaning treatment: sequentially polishing the surface of the substrate by using 400, 800, 1200, 1500 and 2000# SiC sand paper, placing the polished aluminum alloy sample into acetone, cleaning and degreasing under ultrasonic waves, flushing by using absolute ethyl alcohol and deionized water, and drying by using nitrogen to be used.
(b) Surface anodizing: and (3) carrying out surface anodic oxidation treatment by using 27.5g/L phosphoric acid and 22.5g/L oxalic acid as electrolyte, wherein the anodic oxidation treatment voltage is 30V, the time is 810s, and after the power supply is cut off, the solution is put into a 5% phosphoric acid solution for 7min, taken out and rinsed by deionized water.
(c) And (5) nitrogen purging and drying.
The weight portions of the components are as follows:
37.5 parts of water-based saturated polyester resin;
crosslinking agent amino resin: 17.5 parts of highly alkyl etherified benzomelamine resin;
10 parts of iron oxide black;
0.6 part of composite ferrotitanium powder;
0.5 part of HT-100 dispersing wetting agent;
0.26 parts of water-based organic silicon defoamer;
0.4 parts of butynediol penetrant;
0.3 parts of propylene glycol penetration auxiliary;
1.3 parts of pH regulator;
57.5 parts of deionized water.
And (3) taking the aluminum alloy prepared in the step (2) as a base material, coating the water-based paint prepared in the step (1) on the surface of the aluminum alloy, drying the surface of the coating film for 0.75h at normal temperature, then baking for 17min at 160 ℃, and cooling.
Comparative example 2
A water-based paint composition is prepared by the steps of weighing iron oxide black, composite iron titanium powder, a dispersing wetting agent, a penetrating aid and half of water according to mass ratio, uniformly stirring to prepare a dispersion liquid for later use, weighing polyester resin, placing the polyester resin into a stirring kettle, adding a cross-linking agent amino resin curing agent, a water-based organic silicon defoaming agent, the dispersion liquid prepared in the previous step and the other half of water, adding a pH regulator, dispersing for 25 minutes at a speed of 1000rpm, filtering and packaging to obtain the required water-based paint, wherein the water-based paint is coated on the surface of an aluminum alloy subjected to surface treatment, and the surface of the aluminum alloy is a conical porous oxide film, and is obtained by the following steps:
(a) Surface cleaning treatment: sequentially polishing the surface of the substrate by using 400, 800, 1200, 1500 and 2000# SiC sand paper, placing the polished aluminum alloy sample into acetone, cleaning and degreasing under ultrasonic waves, flushing by using absolute ethyl alcohol and deionized water, and drying by using nitrogen to be used.
(b) Surface anodizing: the surface anodic oxidation treatment is carried out by taking mixed solution of phosphoric acid, oxalic acid, citric acid, aluminum oxalate and glycol as electrolyte, and the anodic oxidation treatment process comprises the following steps:
and (b-1) controlling the primary voltage to be two-stage voltage, wherein the first stage voltage is 35V, the duration is 120s, the second stage voltage is 29V, the duration is 120s, the temperature is 5 ℃, and the second stage voltage is 10s after the power supply is cut off, the second stage voltage is put into 5% phosphoric acid solution to be soaked for 3min, taken out, washed by deionized water and soaked into electrolyte.
And (b-3) controlling the secondary voltage to be two-stage voltage, wherein the first stage voltage is 18V, the duration is 60s, the second stage voltage is 15V, the duration is 60s, the temperature is 15 ℃, and the second stage voltage is 10s after the power supply is cut off, the second stage voltage is put into 5% phosphoric acid solution for soaking for 5min, and then taken out and washed by deionized water.
Wherein the concentration of phosphoric acid is 27.5g/L, the concentration of oxalic acid is 22.5g/L, the concentration of citric acid is 7g/L, the concentration of aluminum oxalate is 3g/L, and the concentration of ethylene glycol is 6ml/L.
(c) And (5) nitrogen purging and drying.
The weight portions of the components are as follows:
37.5 parts of water-based saturated polyester resin;
crosslinking agent amino resin: 17.5 parts of highly alkyl etherified benzomelamine resin;
10 parts of iron oxide black;
0.6 part of composite ferrotitanium powder;
0.5 part of HT-100 dispersing wetting agent;
0.26 parts of water-based organic silicon defoamer;
0.4 parts of butynediol penetrant;
0.3 parts of propylene glycol penetration auxiliary;
1.3 parts of pH regulator;
57.5 parts of deionized water.
And (3) taking the aluminum alloy prepared in the step (2) as a base material, coating the water-based paint prepared in the step (1) on the surface of the aluminum alloy, drying the surface of the coating film for 0.75h at normal temperature, then baking for 17min at 160 ℃, and cooling.
Comparative example 3
A water-based paint composition is prepared by the steps of weighing iron oxide black, composite iron titanium powder, a dispersing wetting agent, a penetrating aid and half of water according to mass ratio, uniformly stirring to prepare a dispersion liquid for later use, weighing polyester resin, placing the polyester resin into a stirring kettle, adding a cross-linking agent amino resin curing agent, a water-based organic silicon defoaming agent, the dispersion liquid prepared in the previous step and the other half of water, adding a pH regulator, dispersing for 25 minutes at a speed of 1000rpm, filtering and packaging to obtain the required water-based paint, wherein the water-based paint is coated on the surface of an aluminum alloy subjected to surface treatment, and the surface of the aluminum alloy is a conical porous oxide film, and is obtained by the following steps:
(a) Surface cleaning treatment: sequentially polishing the surface of the substrate by using 400, 800, 1200, 1500 and 2000# SiC sand paper, placing the polished aluminum alloy sample into acetone, cleaning and degreasing under ultrasonic waves, flushing by using absolute ethyl alcohol and deionized water, and drying by using nitrogen to be used.
(b) Surface anodizing: the surface anodic oxidation treatment is carried out by taking mixed solution of phosphoric acid, oxalic acid, citric acid, aluminum oxalate and glycol as electrolyte, and the anodic oxidation treatment process comprises the following steps:
and (b-1) controlling the primary voltage to be three-stage voltage, wherein the first stage voltage is 40V, the duration is 120s, the second stage voltage is 34V, the duration is 120s, the third stage voltage is 28V, the duration is 120s, the temperature is 15 ℃, and the third stage voltage is 10s after the power supply is cut off, the third stage voltage is put into 5% phosphoric acid solution for soaking for 7min, taken out, rinsed by deionized water and soaked into electrolyte.
Controlling the secondary voltage to be three-stage voltage, wherein the first stage voltage is 32V, the duration is 90s, the second stage voltage is 26V, the duration is 90s, the third stage voltage is 21V, the duration is 90s, the temperature is 20 ℃, and the second stage voltage is 10s after the power supply is cut off, the second stage voltage is put into 5% phosphoric acid solution for 7min, taken out, rinsed by deionized water and immersed into electrolyte.
And (b-3) controlling the three voltages to be three-stage voltages, wherein the first stage is 23V, the duration is 60s, the second stage is 20V, the duration is 60s, the third stage is 17V, the duration is 60s, the temperature is 25 ℃, and the third stage is 10s after the power supply is cut off, the third stage is put into 5% phosphoric acid solution to be soaked for 7min, and then taken out and washed by deionized water.
Wherein the concentration of phosphoric acid is 27.5g/L, the concentration of oxalic acid is 22.5g/L, the concentration of citric acid is 7g/L, the concentration of aluminum oxalate is 3g/L, and the concentration of ethylene glycol is 6ml/L.
(c) And (5) nitrogen purging and drying.
The weight portions of the components are as follows:
37.5 parts of water-based saturated polyester resin;
crosslinking agent amino resin: 17.5 parts of highly alkyl etherified benzomelamine resin;
10 parts of iron oxide black;
0.6 part of composite ferrotitanium powder;
0.5 part of HT-100 dispersing wetting agent;
0.26 parts of water-based organic silicon defoamer;
0.4 parts of butynediol penetrant;
0.3 parts of propylene glycol penetration auxiliary;
1.3 parts of pH regulator;
57.5 parts of deionized water.
And (3) taking the aluminum alloy prepared in the step (2) as a base material, coating the water-based paint prepared in the step (1) on the surface of the aluminum alloy, drying the surface of the coating film for 0.75h at normal temperature, then baking for 17min at 160 ℃, and cooling.
The blank test is to directly coat the surface of the aluminum material subjected to surface pretreatment with the coating prepared in example 2.
The bonding strength of the examples and comparative examples of the present invention was tested by using a tensile tester at 20℃and 35% humidity with reference to GB/T5210-1985 until the polymer film was pulled off the substrate, and the maximum force Fmax in the secondary process was measured by using software and calculated according to the formula P=F/S.
Stability test: placing a sample in deionized water, then performing ultrasonic treatment for 30min, controlling the power to be 60W, the frequency to be 40KHz, controlling the temperature to be 30 ℃, then performing salt spray test for 600h, and imaging the corrosion position to be black.
The bonding strength of the coating layers of different coating thicknesses was tested in the present invention of example 2 and comparative examples 1 to 3 and blank example, as shown in fig. 6, wherein the bonding strength of the coating layer of 15 μm was optimal, 22.5MPa, which is far higher than that of the conventional coating layer of comparative example 1 and 6.2MPa for the blank aluminum alloy coating layer, and the bonding strength of comparative example 1 was lower, mainly because the pore diameter of the conventional prepared aluminum alloy was nano-pores, the pore channel array was uniform, as shown in fig. 1, and the pore channels were only about 50 to 70nm, and the coating material was required to overcome extremely high capillary effect to enter the pore channels at such a small pore diameter adjustment, so the bonding strength of comparative example 1 was only 8.2MPa, but since the anodized roughness was significantly higher than that of the surface-cleaned aluminum alloy, and the bonding strength of comparative example 1 was higher than that of the blank example.
In addition, the bonding strength of comparative example 2 and comparative example 3 is not significantly different, as shown in fig. 2 and 3, comparative example 2 is insufficient in corrosion, comparative example 3 is transitional corrosion, two-stage depressurization and two-stage voltage in comparative example 2 result in a very significant shielding layer, and the duct has a significant non-corrosion phenomenon, and comparative example 3 has a significant frontal taper void, but has a significant transitional corrosion, which results in a bonding strength inferior to that of example 2.
In addition, for stability test, the invention carries out ultrasonic oscillation treatment on the aluminum alloy coating in advance, if the bonding force of the coating is not strong, local separation of the coating can occur, and then salt spray test is carried out on the coating, so that the stability of the coating is obviously shown, the corrosion sites of the coating are very small and uniformly distributed on the left top of FIG. 7, namely, the bonding force of the coating and a base material of the invention is effectively proved to be stable, the bonding force of each site is basically consistent, and the uniformity is extremely good. In contrast, the upper right of fig. 7, the lower left of fig. 7, and the lower right of fig. 7 correspond to the respective comparative examples 1 to 3, and the coating effect of the present invention is inferior in terms of both the bonding force and the uniformity of the bonding force.
Although the present invention has been described by way of example with reference to the preferred embodiments, the present invention is not limited to the specific embodiments, and may be modified appropriately within the scope of the present invention.
Claims (2)
1. The conical porous oxide film coated water-based paint composition is characterized by comprising the following raw materials in parts by mass:
35-40 parts of water-based saturated polyester resin;
15-20 parts of cross-linking agent amino resin;
7-13 parts of iron oxide black;
0.4-0.8 part of composite ferrotitanium powder;
0.3-0.7 part of dispersing wetting agent;
0.2-0.35 part of water-based organic silicon defoamer;
0.3-0.5 part of butynediol penetrant;
0.2-0.4 part of propylene glycol penetration auxiliary agent;
1-1.6 parts of pH regulator;
50-65 parts of deionized water;
wherein the mass ratio of the water-based saturated polyester resin to the amino resin is 1-3.5:1;
the cross-linking agent amino resin is selected from the group consisting of highly alkyl etherified benzomelamine resins;
the dispersing wetting agent is selected from HT-100 succinate block copolymers;
the coating is coated on the surface of the aluminum alloy subjected to surface treatment, and the surface of the aluminum alloy is a conical porous oxide film, and the aluminum alloy is obtained by the following method
(a) Surface cleaning treatment: sequentially polishing the surface of a substrate by using 400, 800, 1200, 1500 and 2000# SiC sand paper, placing a polished aluminum alloy sample into acetone, cleaning and degreasing under ultrasonic waves, flushing by using absolute ethyl alcohol and deionized water, and blowing and drying by using nitrogen for standby;
(b) Surface anodizing: the surface anodic oxidation treatment is carried out by taking mixed solution of phosphoric acid, oxalic acid, citric acid, aluminum oxalate and glycol as electrolyte, and the anodic oxidation treatment process comprises the following steps:
(b-1) controlling the primary voltage to be three-stage voltage, wherein the first stage voltage is 35V, the duration is 120s, the second stage voltage is 29V, the duration is 120s, the third stage voltage is 23V, the duration is 120s, the temperature is 5 ℃, and after the power supply is cut off, the three-stage voltage is 10s, the three-stage voltage is put into 5% phosphoric acid solution to be soaked for 3min, and the three-stage voltage is taken out, washed by deionized water and soaked into electrolyte;
(b-2) controlling the secondary voltage to be three-stage voltage, wherein the first stage voltage is 27V, the duration is 90s, the second stage voltage is 21V, the duration is 90s, the third stage voltage is 16V, the duration is 90s, the temperature is 10 ℃, and after the power supply is cut off, the three-stage voltage is 10s and then is put into 5% phosphoric acid solution to be soaked for 4min, and the three-stage voltage is taken out, washed by deionized water and soaked into electrolyte;
(b-3) controlling the three voltages to be three-stage voltages, wherein the first stage is 18V, the duration is 60s, the second stage is 15V, the duration is 60s, the third stage is 12V, the duration is 60s, the temperature is 15 ℃, and the third stage is 10s after the power supply is cut off, the third stage is put into 5% phosphoric acid solution to be soaked for 5min, and then taken out and washed by deionized water;
wherein the concentration of phosphoric acid is 25-30g/L, the concentration of oxalic acid is 25-20g/L, the concentration of citric acid is 6-8g/L, the concentration of aluminum oxalate is 2-4/L, and the concentration of ethylene glycol is 5-7ml/L;
(c) Nitrogen purging and drying;
the binding force between the paint and the aluminum alloy substrate is 16.3-22.5Mpa.
2. A tapered porous oxide film coated aqueous coating composition according to claim 1, wherein said pH adjuster is selected from the group consisting of glycol amines.
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| CN115672704B (en) * | 2022-12-07 | 2024-03-01 | 德瑞宝(中国)复合材料有限公司 | Water-based paint coating process |
| CN115895408B (en) * | 2022-12-29 | 2024-06-07 | 广东德普威涂料有限公司 | Water-based paint composition |
| CN115895407B (en) * | 2022-12-29 | 2023-11-10 | 江苏云丝亮新材料科技有限公司 | Preparation method of high-performance water-based paint |
| CN116410660B (en) * | 2023-03-09 | 2025-01-14 | 江西坤隆新材料有限公司 | Preparation method of water-based paint composite material |
| CN116254046B (en) * | 2023-03-09 | 2024-05-10 | 金万正(广东)新材料有限公司 | UV (ultraviolet) coating |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6335670A (en) * | 1986-07-30 | 1988-02-16 | Canon Inc | Semisolid ink |
| JP2001131471A (en) * | 1999-11-02 | 2001-05-15 | Teijin Ltd | Surface coating liquid and method for preparing the same |
| WO2010017069A1 (en) * | 2008-08-07 | 2010-02-11 | 3M Innovative Properties Company | Acicular silica coating for enhanced hydrophilicity/transmittivity |
| CN102181220A (en) * | 2011-01-19 | 2011-09-14 | 天津滨新涂料有限公司 | Novel environment-friendly waterborne baking varnish for coiled material |
| CN105088310A (en) * | 2015-09-21 | 2015-11-25 | 天津工业大学 | Preparation method of conical anodized aluminum oxide template |
| CN106433416A (en) * | 2016-10-13 | 2017-02-22 | 广州立邦涂料有限公司 | High temperature-resistant primer, and preparation method and application thereof |
| CN107709483A (en) * | 2015-05-29 | 2018-02-16 | Prc-迪索托国际公司 | Metal base containing lithium metasilicate as the curable film-forming composition and multiple coating of corrosion inhibitor |
| CN108863075A (en) * | 2018-07-20 | 2018-11-23 | 吴伟华 | A kind of enamel coating and application method |
| CN109370351A (en) * | 2018-10-25 | 2019-02-22 | 陈换换 | A kind of environment-friendly water-based diatom ooze coating and preparation method thereof |
| CN112813476A (en) * | 2020-12-30 | 2021-05-18 | 杭州电子科技大学 | Method for preparing conical AAO by alternately performing anodic oxidation and phosphoric acid hole expansion |
| CN113881337A (en) * | 2021-10-19 | 2022-01-04 | 中国科学院宁波材料技术与工程研究所 | A kind of high temperature resistant light absorption coating and preparation method thereof |
| CN114561684A (en) * | 2021-12-29 | 2022-05-31 | 深圳市鑫鸿达清洗技术有限公司 | Stainless steel-aluminum alloy composite material and surface pore-forming method thereof |
-
2022
- 2022-09-11 CN CN202211106373.8A patent/CN115403993B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6335670A (en) * | 1986-07-30 | 1988-02-16 | Canon Inc | Semisolid ink |
| JP2001131471A (en) * | 1999-11-02 | 2001-05-15 | Teijin Ltd | Surface coating liquid and method for preparing the same |
| WO2010017069A1 (en) * | 2008-08-07 | 2010-02-11 | 3M Innovative Properties Company | Acicular silica coating for enhanced hydrophilicity/transmittivity |
| CN102181220A (en) * | 2011-01-19 | 2011-09-14 | 天津滨新涂料有限公司 | Novel environment-friendly waterborne baking varnish for coiled material |
| CN107709483A (en) * | 2015-05-29 | 2018-02-16 | Prc-迪索托国际公司 | Metal base containing lithium metasilicate as the curable film-forming composition and multiple coating of corrosion inhibitor |
| CN105088310A (en) * | 2015-09-21 | 2015-11-25 | 天津工业大学 | Preparation method of conical anodized aluminum oxide template |
| CN106433416A (en) * | 2016-10-13 | 2017-02-22 | 广州立邦涂料有限公司 | High temperature-resistant primer, and preparation method and application thereof |
| CN108863075A (en) * | 2018-07-20 | 2018-11-23 | 吴伟华 | A kind of enamel coating and application method |
| CN109370351A (en) * | 2018-10-25 | 2019-02-22 | 陈换换 | A kind of environment-friendly water-based diatom ooze coating and preparation method thereof |
| CN112813476A (en) * | 2020-12-30 | 2021-05-18 | 杭州电子科技大学 | Method for preparing conical AAO by alternately performing anodic oxidation and phosphoric acid hole expansion |
| CN113881337A (en) * | 2021-10-19 | 2022-01-04 | 中国科学院宁波材料技术与工程研究所 | A kind of high temperature resistant light absorption coating and preparation method thereof |
| CN114561684A (en) * | 2021-12-29 | 2022-05-31 | 深圳市鑫鸿达清洗技术有限公司 | Stainless steel-aluminum alloy composite material and surface pore-forming method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 汽车中层涂料的研究――性能要求、原料选择与配方平衡;郑炜;上海涂料(第1期);7-11 * |
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