CN115216759B - Hydrophilic chemical conversion film forming liquid and aluminum alloy surface treatment method - Google Patents
Hydrophilic chemical conversion film forming liquid and aluminum alloy surface treatment method Download PDFInfo
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- CN115216759B CN115216759B CN202210804004.XA CN202210804004A CN115216759B CN 115216759 B CN115216759 B CN 115216759B CN 202210804004 A CN202210804004 A CN 202210804004A CN 115216759 B CN115216759 B CN 115216759B
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 99
- 239000000126 substance Substances 0.000 title claims abstract description 91
- 229910000838 Al alloy Inorganic materials 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000007788 liquid Substances 0.000 title claims abstract description 25
- 238000004381 surface treatment Methods 0.000 title claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 53
- 230000032683 aging Effects 0.000 claims abstract description 25
- 239000002253 acid Substances 0.000 claims abstract description 19
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 16
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 16
- 239000000654 additive Substances 0.000 claims abstract description 10
- 230000000996 additive effect Effects 0.000 claims abstract description 10
- 239000008139 complexing agent Substances 0.000 claims abstract description 10
- 150000001844 chromium Chemical class 0.000 claims abstract description 9
- 238000004140 cleaning Methods 0.000 claims abstract description 9
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 3
- 239000012535 impurity Substances 0.000 claims abstract description 3
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims description 51
- 239000008367 deionised water Substances 0.000 claims description 36
- 229910021641 deionized water Inorganic materials 0.000 claims description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 238000005238 degreasing Methods 0.000 claims description 27
- 238000007789 sealing Methods 0.000 claims description 25
- 239000011248 coating agent Substances 0.000 claims description 21
- 238000000576 coating method Methods 0.000 claims description 21
- 239000003513 alkali Substances 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 10
- 230000002378 acidificating effect Effects 0.000 claims description 10
- 229910000077 silane Inorganic materials 0.000 claims description 10
- 239000012459 cleaning agent Substances 0.000 claims description 9
- 238000005554 pickling Methods 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 5
- 229910021555 Chromium Chloride Inorganic materials 0.000 claims description 4
- 239000002981 blocking agent Substances 0.000 claims description 4
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 4
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 claims description 2
- BJZIJOLEWHWTJO-UHFFFAOYSA-H dipotassium;hexafluorozirconium(2-) Chemical compound [F-].[F-].[F-].[F-].[F-].[F-].[K+].[K+].[Zr+4] BJZIJOLEWHWTJO-UHFFFAOYSA-H 0.000 claims description 2
- RXCBCUJUGULOGC-UHFFFAOYSA-H dipotassium;tetrafluorotitanium;difluoride Chemical group [F-].[F-].[F-].[F-].[F-].[F-].[K+].[K+].[Ti+4] RXCBCUJUGULOGC-UHFFFAOYSA-H 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 abstract description 20
- 230000007797 corrosion Effects 0.000 abstract description 16
- 238000001179 sorption measurement Methods 0.000 abstract description 8
- 229910017053 inorganic salt Inorganic materials 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 231100000086 high toxicity Toxicity 0.000 abstract description 2
- 229910052782 aluminium Inorganic materials 0.000 description 108
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 108
- 239000011888 foil Substances 0.000 description 107
- 238000007605 air drying Methods 0.000 description 16
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- 239000007864 aqueous solution Substances 0.000 description 14
- 239000011651 chromium Substances 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000004448 titration Methods 0.000 description 4
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 3
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 238000007739 conversion coating Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000007888 film coating Substances 0.000 description 2
- 238000009501 film coating Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- -1 rare earth salt Chemical class 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000004372 laser cladding Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000007745 plasma electrolytic oxidation reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
- C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
- C23C22/361—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing titanium, zirconium or hafnium compounds
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/78—Pretreatment of the material to be coated
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/12—Light metals
- C23G1/125—Light metals aluminium
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
- C23G1/22—Light metals
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
The invention relates to a hydrophilic chemical conversion film forming liquid and an aluminum alloy surface treatment method. Hydrophilic chemical conversion film forming liquid comprising trivalent chromium salt, fluorozirconate, organic complexing agent, inorganic salt additive and water; the organic complexing agent is one or more of polyvinyl alcohol, polyethylene glycol and polyacrylamide; the inorganic salt additive is fluotitanic acid and/or fluotitanate. The invention also provides an aluminum alloy surface treatment method, which comprises the following steps: removing impurities from the surface of the aluminum alloy; placing aluminum alloy into the hydrophilic chemical conversion film forming liquid to perform chemical conversion treatment so as to form a hydrophilic chemical conversion film on the surface of the aluminum alloy; and (3) cleaning the coated aluminum alloy, and naturally aging in a normal-temperature environment. The invention effectively improves the adsorption capacity of the metal surface, and solves the problems of high toxicity, poor corrosion resistance, complex working procedure and poor protection effect of the existing aluminum alloy surface chemical conversion film.
Description
Technical Field
The invention relates to the technical field of aluminum alloy surface treatment, in particular to a hydrophilic chemical conversion film forming liquid and an aluminum alloy surface treatment method.
Background
Aluminum alloys are the most widely used lightweight metallic structural materials in the world today. In order to meet the requirements of mechanical properties and the like, a plurality of alloy elements such as Cu, mg, zn, si and the like are generally added into the aluminum alloy. However, the corrosion resistance of most aluminum alloys is reduced due to the addition of a large amount of alloying elements, and the requirements of industrial applications cannot be met. Therefore, most aluminum alloys require a certain surface treatment to be put into service.
Common aluminum alloy surface treatment processes include: electroplating, chemical conversion, anodic oxidation, micro-arc oxidation, laser cladding, sol-gel, and the like. The chemical conversion coating treatment does not need an external power supply, has the advantages of simple process operation, low production cost, no obvious influence on the mechanical properties of the base material and the like, and is widely applied to industrial production. Among them, the chromate conversion film is the chemical conversion film which is the longest in use, the best in corrosion resistance, and has a self-healing function, and has been widely used for a long time in the past.
However, long-term practical research shows that hexavalent chromium ions contained in chromates have carcinogenicity and are seriously harmful to human bodies, animals and natural environments. The European Union environmental protection organization comprehensively prohibits the commercial application of hexavalent chromium conversion coatings in 2017, and countries such as America, the day and the like have stricter restrictions on hexavalent chromium. Thus, green and environment-friendly chromium-free conversion and chemical conversion processes have been developed. The chromium-free conversion film mainly comprises zirconate, phosphate, molybdate, titanate, cobaltate, rare earth salt conversion film and the like, but the chromium-free conversion film is loose and has poor corrosion resistance or complex working procedure, and the protective effect and the application range are not as good as those of the chromate conversion film.
Disclosure of Invention
The invention aims to provide a hydrophilic chemical conversion film-forming liquid so as to improve the adsorption capacity of a metal surface; the second aim is to provide a surface treatment method of aluminum alloy to improve the adsorption performance of the surface of aluminum alloy, and also to solve the problems of high toxicity, poor corrosion resistance, complicated working procedure and poor protection effect of the existing chemical conversion film on the surface of aluminum alloy.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a hydrophilic chemical conversion film-forming liquid, which comprises trivalent chromium salt, fluorozirconate, organic complexing agent, inorganic salt additive and water;
the organic complexing agent is one or more of polyvinyl alcohol, polyethylene glycol and polyacrylamide;
the inorganic salt additive is fluotitanic acid (H) 2 TiF 6 ) And/or fluorotitanates.
Preferably, the trivalent chromium salt comprises chromium sulfate (Cr 2 (SO 4 ) 3 ) Chromium nitrate (Cr (NO) 3 ) 3 ) And chromium chloride (CrCl) 3 ) One or more of the following.
Preferably, the fluorozirconate comprises potassium fluorozirconate (K 2 ZrF 6 ) And sodium fluorozirconate (Na 2 ZrF 6 ) One or two of them.
Preferably, the fluorotitanate is potassium fluorotitanate (K 2 TiF 6 )。
Preferably, the concentration of the trivalent chromium salt is 0.5-5 g/L, the concentration of the fluorozirconate is 1-10 g/L, the concentration of the organic complexing agent is 2-10 g/L, and the concentration of the inorganic salt additive is 0.5-5 g/L.
The invention also provides an aluminum alloy surface treatment method, which comprises the following steps:
s1, pretreatment: removing impurities from the surface of the aluminum alloy;
s2, coating: adjusting the pH value of the hydrophilic chemical conversion film-forming liquid to be acidic, and placing the aluminum alloy into the acidic hydrophilic chemical conversion film-forming liquid for chemical conversion treatment so as to form a hydrophilic chemical conversion film on the surface of the aluminum alloy;
s3, natural aging: cleaning the coated aluminum alloy, and naturally aging in a normal temperature environment.
Preferably, after natural aging, the method further comprises an organic sealing treatment, specifically: and sealing the naturally aged aluminum alloy in an organic sealing agent.
According to the technical means, after film coating and natural aging, namely, after priming treatment is carried out on the surface of the aluminum alloy, sealing treatment is carried out, so that the corrosion resistance of the aluminum alloy is greatly improved, wherein the film coating is carried out on the surface of the aluminum alloy through the hydrophilic chemical conversion film forming liquid, the adsorption capacity of the aluminum alloy to the organic sealing agent is effectively improved, and the corrosion resistance of the aluminum alloy is further improved.
Preferably, in the step S2, the temperature of the chemical conversion treatment is 20-60 ℃, and the film forming rate can be controlled in the temperature range, so that the film layer can grow rapidly and uniformly, and the time of the chemical conversion treatment is 60-600 seconds.
Preferably, in the step S1, the pretreatment includes sequentially degreasing, alkaline washing, acid washing and rinsing the aluminum alloy;
wherein, the degreasing adopts degreasing cleaning agent to carry out cleaning treatment, the cleaning temperature is 50 ℃ to 60 ℃ and the cleaning time is 30 to 120 seconds; alkali washing (to sufficiently remove the surface rolling deformation layer and part of second phase particles) is carried out by adopting 5-10% (wt.) sodium hydroxide (NaOH) solution, the alkali washing temperature is 30-40 ℃, and the alkali washing time is 10-60 seconds; the pickling adopts 30 to 40 percent (vol.) nitric acid (HNO) 3 ) Treating the solution, wherein the pickling temperature is 20-30 ℃, and the pickling time is 10-60 seconds; the rinsing is carried out by deionized water, the rinsing temperature is 70-80 ℃, and the rinsing time is 10-60 seconds.
Preferably, in the step S3, the natural aging time is 4 to 24 hours.
Preferably, the organic blocking agent is a silane blocking agent.
Preferably, the thickness of the chemical conversion film formed on the surface of the aluminum alloy is 50 nm-150 nm, and the water contact angle of the chemical conversion film is less than 50 degrees.
The invention has the beneficial effects that:
1) According to the hydrophilic chemical conversion film forming liquid, chromium salt, fluorozirconate, an organic complexing agent and an inorganic salt additive are used as main components of the film forming liquid, the chromium salt has the advantages of low toxicity, good corrosion resistance, high temperature resistance, certain conductivity and good adhesive force, the fluorozirconate is used as an oxidant and a film forming agent and is mainly used for providing fluoride ions to dissolve an aluminum matrix so as to promote the film forming reaction, the organic complexing agent can prevent the hydrolysis of trivalent chromium, the deposition speed of metal ions can be stabilized and controlled in a certain pH range, the hydrophilicity of a film layer can be improved, the inorganic salt additive is a film forming accelerator, the structure of a passivation film layer is fine, the porosity is reduced, and meanwhile, more stable oxide is introduced into the film layer, so that the nano chemical conversion film prepared on the metal surface has good hydrophilic property, the adsorption property on the metal surface is effectively improved, and good preconditions are provided for adsorbing a sealing agent on the metal surface;
2) According to the aluminum alloy surface treatment method, the aluminum alloy is placed into the hydrophilic chemical conversion film forming liquid, so that the chemical conversion film forming liquid and the surface of the aluminum alloy are subjected to chemical reaction, a layer of chemical conversion film is formed on the surface of the aluminum alloy, experimental research proves that the chemical conversion film formed on the surface of the aluminum alloy has good hydrophilic performance, the adsorption performance of the surface of the aluminum alloy is obviously improved, a good foundation is provided for the subsequent organic sealing treatment, and the preparation method has the advantages of simple working procedure, mild condition, short film forming time, environmental protection and low production cost, is suitable for industrial production, and has popularization and application values in the technical field of aluminum alloy surface treatment.
Drawings
FIG. 1 is a scanning electron microscope topography (10 μm) of 5056 aluminum foil treated in examples 1-4;
FIG. 2 is a scanning electron microscope topography (1 μm) of 5056 aluminum foil treated in examples 1 to 4;
FIG. 3 is a graph of the macroscopic morphology of the 5056 aluminum foil treated in examples 1 and 4 after 5% neutral salt spray test;
fig. 4 is a graph showing the results of water contact angle tests performed on the 5056 aluminum foil treated in example 1, example 2, example 4 and comparative example 1;
FIG. 5 is a graph showing the electrochemical polarization of the 5056 aluminum foil treated in examples 1 to 3 measured in 3.5% (wt%) aqueous NaCl solution;
FIG. 6 is a graph showing the results of a potassium dichromate drop test of an uncoated 5056 aluminum foil and a 5056 aluminum foil treated in example 1, example 5 and example 6;
fig. 7 is a graph showing the results of the potassium dichromate drop test performed on 5056 aluminum foil treated in example 4 and comparative example 1.
Detailed Description
Further advantages and effects of the present invention will become readily apparent to those skilled in the art from the disclosure herein, by referring to the accompanying drawings and the preferred embodiments. The invention may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present invention. It should be understood that the preferred embodiments are presented by way of illustration only and not by way of limitation.
Example 1
An aluminum alloy surface treatment method comprises the following steps:
s1, pretreatment:
1) Oil removal treatment: putting the whole 5056 aluminum foil into 10wt.% degreasing cleaning agent, keeping the temperature at 60 ℃ for 30s to perform degreasing and degreasing treatment, taking out, and rinsing in 80 ℃ deionized water for 30s;
2) Alkali washing treatment: putting the 5056 aluminum foil subjected to oil removal treatment into a 10wt.% NaOH aqueous solution, keeping the constant temperature at 40 ℃ for 30s, taking out, and rinsing in deionized water at 80 ℃ for 30s;
3) Acid washing: the 5056 aluminum foil after alkali washing treatment is put into 30vol.% HNO 3 Carrying out deoxidation and ash removal treatment for 30s in the aqueous solution, and then taking out and rinsing in deionized water at 80 ℃ for 30s;
4) And (3) rinsing: washing the 5056 aluminum foil subjected to acid washing treatment by deionized water, and finally naturally air-drying to obtain a pretreated 5056 aluminum foil;
s2, coating: with 1wt.% of H 2 SO 4 The pH value of the hydrophilic chemical conversion film forming solution is regulated to 3.5, the 5056 aluminum foil subjected to pretreatment in the step S1 is placed into the acidic hydrophilic chemical conversion film forming solution to be subjected to chemical conversion treatment, so that a hydrophilic chemical conversion film is formed on the surface of the 5056 aluminum foil, the temperature of the chemical conversion treatment is 40 ℃, and the time of the chemical conversion treatment is 90S;
wherein the hydrophilic chemical conversion film-forming liquid in this example 1 contains Cr as a component 2 (SO 4 ) 3 、K 2 ZrF 6 Polyvinyl alcohol, H 2 TiF 6 And water, cr 2 (SO 4 ) 3 Is 2g/L, K 2 ZrF 6 The concentration of (C) is 4g/L, the concentration of polyvinyl alcohol is 6g/L, H 2 TiF 6 Is 2g/L;
s3, natural aging: and (3) washing the 5056 aluminum foil with deionized water after coating, and then naturally air-drying and aging for 8 hours in a normal temperature environment to obtain the 5056 aluminum foil with the colorless chemical conversion film formed on the surface.
Example 2
An aluminum alloy surface treatment method comprises the following steps:
s1, pretreatment:
1) Oil removal treatment: putting the whole 5056 aluminum foil into 10wt.% degreasing cleaning agent, keeping the temperature at 60 ℃ for 30s to perform degreasing and degreasing treatment, taking out, and rinsing in 80 ℃ deionized water for 30s;
2) Alkali washing treatment: putting the 5056 aluminum foil subjected to oil removal treatment into a 10wt.% NaOH aqueous solution, keeping the constant temperature at 40 ℃ for 30s, taking out, and rinsing in deionized water at 80 ℃ for 30s;
3) Acid washing: the 5056 aluminum foil after alkali washing treatment is put into 30vol.% HNO 3 Carrying out deoxidation and ash removal treatment for 30s in the aqueous solution, and then taking out and rinsing in deionized water at 80 ℃ for 30s;
4) And (3) rinsing: washing the 5056 aluminum foil subjected to acid washing treatment by deionized water, and finally naturally air-drying to obtain a pretreated 5056 aluminum foil;
s2, coating: with 1wt.% of H 2 SO 4 The pH value of the hydrophilic chemical conversion film forming solution is regulated to 4.5, the 5056 aluminum foil subjected to pretreatment in the step S1 is placed into the acidic hydrophilic chemical conversion film forming solution to be subjected to chemical conversion treatment, so that a hydrophilic chemical conversion film is formed on the surface of the 5056 aluminum foil, the temperature of the chemical conversion treatment is 40 ℃, and the time of the chemical conversion treatment is 90S;
wherein the hydrophilic chemical conversion film-forming liquid in this example 2 had a composition of Cr (NO 3 ) 3 、Na 2 ZrF 6 Polyvinyl alcohol, H 2 TiF 6 And water, cr (NO) 3 ) 3 Is 2g/L, na 2 ZrF 6 The concentration of (C) is 4g/L, the concentration of polyvinyl alcohol is 6g/L, H 2 TiF 6 Is 2g/L;
s3, natural aging: and (3) washing the 5056 aluminum foil with deionized water after coating, and then naturally air-drying and aging for 8 hours in a normal temperature environment to obtain the 5056 aluminum foil with the colorless chemical conversion film formed on the surface.
Example 3
An aluminum alloy surface treatment method comprises the following steps:
s1, pretreatment:
1) Oil removal treatment: putting the whole 5056 aluminum foil into 10wt.% degreasing cleaning agent, keeping the temperature at 60 ℃ for 30s to perform degreasing and degreasing treatment, taking out, and rinsing in 80 ℃ deionized water for 30s;
2) Alkali washing treatment: putting the 5056 aluminum foil subjected to oil removal treatment into a 10wt.% NaOH aqueous solution, keeping the constant temperature at 40 ℃ for 30s, taking out, and rinsing in deionized water at 80 ℃ for 30s;
3) Acid washing: the 5056 aluminum foil after alkali washing treatment is put into 30vol.% HNO 3 Carrying out deoxidation and ash removal treatment for 30s in the aqueous solution, and then taking out and rinsing in deionized water at 80 ℃ for 30s;
4) And (3) rinsing: washing the 5056 aluminum foil subjected to acid washing treatment by deionized water, and finally naturally air-drying to obtain a pretreated 5056 aluminum foil;
s2, coating: with 1wt.% of H 2 SO 4 The pH value of the hydrophilic chemical conversion film forming solution is regulated to 5.5, the 5056 aluminum foil subjected to pretreatment in the step S1 is placed into the acidic hydrophilic chemical conversion film forming solution to be subjected to chemical conversion treatment, so that a hydrophilic chemical conversion film is formed on the surface of the 5056 aluminum foil, the temperature of the chemical conversion treatment is 40 ℃, and the time of the chemical conversion treatment is 90S;
wherein the hydrophilic chemical conversion film-forming liquid in this example 3 has a composition of CrCl 3 、Na 2 ZrF 6 Polyvinyl alcohol, H 2 TiF 6 And water, crCl 3 Is 2g/L, na 2 ZrF 6 The concentration of (C) is 4g/L, the concentration of polyvinyl alcohol is 6g/L, H 2 TiF 6 Is 2g/L;
s3, natural aging: and (3) washing the 5056 aluminum foil with deionized water after coating, and then naturally air-drying and aging for 8 hours in a normal temperature environment to obtain the 5056 aluminum foil with the colorless chemical conversion film formed on the surface.
Example 4
An aluminum alloy surface treatment method comprises the following steps:
s1, pretreatment:
1) Oil removal treatment: putting the whole 5056 aluminum foil into 10wt.% degreasing cleaning agent, keeping the temperature at 60 ℃ for 30s to perform degreasing and degreasing treatment, taking out, and rinsing in 80 ℃ deionized water for 30s;
2) Alkali washing treatment: putting the 5056 aluminum foil subjected to oil removal treatment into a 10wt.% NaOH aqueous solution, keeping the constant temperature at 40 ℃ for 30s, taking out, and rinsing in deionized water at 80 ℃ for 30s;
3) Acid washing: the 5056 aluminum foil after alkali washing treatment is put into 30vol.% HNO 3 Carrying out deoxidation and ash removal treatment for 30s in the aqueous solution, and then taking out and rinsing in deionized water at 80 ℃ for 30s;
4) And (3) rinsing: washing the 5056 aluminum foil subjected to acid washing treatment by deionized water, and finally naturally air-drying to obtain a pretreated 5056 aluminum foil;
s2, coating: with 1wt.% of H 2 SO 4 The pH value of the hydrophilic chemical conversion film forming solution is regulated to 3.5, the 5056 aluminum foil subjected to pretreatment in the step S1 is placed into the acidic hydrophilic chemical conversion film forming solution to be subjected to chemical conversion treatment, so that a hydrophilic chemical conversion film is formed on the surface of the 5056 aluminum foil, the temperature of the chemical conversion treatment is 40 ℃, and the time of the chemical conversion treatment is 90S;
wherein the hydrophilic chemical conversion film-forming liquid in this example 4 contains Cr as a component 2 (SO 4 ) 3 、K 2 ZrF 6 Polyvinyl alcohol, H 2 TiF 6 And water, cr 2 (SO 4 ) 3 Is 2g/L, K 2 ZrF 6 The concentration of (2) g/L, the concentration of polyvinyl alcohol is 6g/L, H 2 TiF 6 Is 2g/L;
s3, natural aging: washing 5056 aluminum foil with deionized water after coating, and then naturally air-drying and aging for 8 hours in a normal temperature environment to obtain 5056 aluminum foil with a colorless chemical conversion film formed on the surface;
s4, placing the 5056 aluminum foil subjected to natural air drying and aging in a silane sealing agent for sealing treatment, taking out, and drying in an oven to obtain the sealed 5056 aluminum foil.
Example 5
An aluminum alloy surface treatment method comprises the following steps:
s1, pretreatment:
5) Oil removal treatment: putting the whole 5056 aluminum foil into 10wt.% degreasing cleaning agent, keeping the temperature at 60 ℃ for 30s to perform degreasing and degreasing treatment, taking out, and rinsing in 80 ℃ deionized water for 30s;
6) Alkali washing treatment: putting the 5056 aluminum foil subjected to oil removal treatment into a 10wt.% NaOH aqueous solution, keeping the constant temperature at 40 ℃ for 30s, taking out, and rinsing in deionized water at 80 ℃ for 30s;
7) Acid washing: the 5056 aluminum foil after alkali washing treatment is put into 30vol.% HNO 3 Deoxidizing and deashing in aqueous solution for 30s, and taking out in deionized water at 80deg.CRinsing for 30s;
8) And (3) rinsing: washing the 5056 aluminum foil subjected to acid washing treatment by deionized water, and finally naturally air-drying to obtain a pretreated 5056 aluminum foil;
s2, coating: with 1wt.% of H 2 SO 4 The pH value of the hydrophilic chemical conversion film forming solution is regulated to 3.5, the 5056 aluminum foil subjected to pretreatment in the step S1 is placed into the acidic hydrophilic chemical conversion film forming solution to be subjected to chemical conversion treatment, so that a hydrophilic chemical conversion film is formed on the surface of the 5056 aluminum foil, the temperature of the chemical conversion treatment is 40 ℃, and the time of the chemical conversion treatment is 90S;
wherein the hydrophilic chemical conversion film-forming liquid in this example 4 contains Cr as a component 2 (SO 4 ) 3 、K 2 ZrF 6 Polyvinyl alcohol, H 2 TiF 6 And water, cr 2 (SO 4 ) 3 Is 0.5g/L, K 2 ZrF 6 The concentration of the polyvinyl alcohol is 1g/L, the concentration of the polyvinyl alcohol is 2g/L, H 2 TiF 6 Is 0.5g/L;
s3, natural aging: washing 5056 aluminum foil with deionized water after coating, and then naturally air-drying and aging for 8 hours in a normal temperature environment to obtain 5056 aluminum foil with a colorless chemical conversion film formed on the surface;
s4, placing the 5056 aluminum foil subjected to natural air drying and aging in a silane sealing agent for sealing treatment, taking out, and drying in an oven to obtain the sealed 5056 aluminum foil.
Example 6
An aluminum alloy surface treatment method comprises the following steps:
s1, pretreatment:
9) Oil removal treatment: putting the whole 5056 aluminum foil into 10wt.% degreasing cleaning agent, keeping the temperature at 60 ℃ for 30s to perform degreasing and degreasing treatment, taking out, and rinsing in 80 ℃ deionized water for 30s;
10 Alkali washing treatment: putting the 5056 aluminum foil subjected to oil removal treatment into a 10wt.% NaOH aqueous solution, keeping the constant temperature at 40 ℃ for 30s, taking out, and rinsing in deionized water at 80 ℃ for 30s;
11 Acid washing treatment: the 5056 aluminum foil after alkali washing treatment is put into 30vol.% HNO 3 Carrying out deoxidation and ash removal treatment for 30s in the aqueous solution, and then taking out and rinsing in deionized water at 80 ℃ for 30s;
12 Rinsing treatment: washing the 5056 aluminum foil subjected to acid washing treatment by deionized water, and finally naturally air-drying to obtain a pretreated 5056 aluminum foil;
s2, coating: with 1wt.% of H 2 SO 4 The pH value of the hydrophilic chemical conversion film forming solution is regulated to 3.5, the 5056 aluminum foil subjected to pretreatment in the step S1 is placed into the acidic hydrophilic chemical conversion film forming solution to be subjected to chemical conversion treatment, so that a hydrophilic chemical conversion film is formed on the surface of the 5056 aluminum foil, the temperature of the chemical conversion treatment is 40 ℃, and the time of the chemical conversion treatment is 90S;
wherein the hydrophilic chemical conversion film-forming liquid in this example 4 contains Cr as a component 2 (SO 4 ) 3 、K 2 ZrF 6 Polyvinyl alcohol, H 2 TiF 6 And water, cr 2 (SO 4 ) 3 Is 5g/L, K 2 ZrF 6 The concentration of the polyvinyl alcohol is 10g/L, H 2 TiF 6 Is 5g/L;
s3, natural aging: washing 5056 aluminum foil with deionized water after coating, and then naturally air-drying and aging for 8 hours in a normal temperature environment to obtain 5056 aluminum foil with a colorless chemical conversion film formed on the surface;
s4, placing the 5056 aluminum foil subjected to natural air drying and aging in a silane sealing agent for sealing treatment, taking out, and drying in an oven to obtain the sealed 5056 aluminum foil.
Comparative example 1
An aluminum alloy surface treatment method comprises the following steps:
s1, pretreatment:
1) Oil removal treatment: putting the whole 5056 aluminum foil into 10wt.% degreasing cleaning agent, keeping the temperature at 60 ℃ for 30s to perform degreasing and degreasing treatment, taking out, and rinsing in 80 ℃ deionized water for 30s;
2) Alkali washing treatment: putting the 5056 aluminum foil subjected to oil removal treatment into a 10wt.% NaOH aqueous solution, keeping the constant temperature at 40 ℃ for 30s, taking out, and rinsing in deionized water at 80 ℃ for 30s;
3) Acid washing: the 5056 aluminum foil after alkali washing treatment is put into 30vol.% HNO 3 Carrying out deoxidation and ash removal treatment for 30s in the aqueous solution, and then taking out and rinsing in deionized water at 80 ℃ for 30s;
4) And (3) rinsing: washing the 5056 aluminum foil subjected to acid washing treatment by deionized water, and finally naturally air-drying to obtain a pretreated 5056 aluminum foil;
s2, directly placing the rinsed and air-dried 5056 aluminum foil in a silane sealing agent for sealing treatment, taking out, and drying in an oven to obtain the sealed 5056 aluminum foil.
Detection analysis
1. Morphology observation
Morphology observation was performed on the 5056 aluminum foils processed in examples 1 to 4 by using a scanning electron microscope, and the results are shown in fig. 1 and 2.
As can be seen from fig. 1 and 2, the chemical conversion films formed on the surfaces of the 5056 aluminum foils treated in examples 1 to 4 were dense and uniform, and the surface of the 5056 aluminum foil pattern showed a small amount of air holes due to the generation of hydrogen gas during the plating process, but the whole was relatively flat, and no defects such as cracking were found.
2. Salt spray test
The aluminum foil 5056 which was not subjected to the plating treatment, the aluminum foils 5056 treated in examples 1 and 4 were subjected to a salt spray test, and the results are shown in fig. 3.
As can be seen from fig. 3, after 48 hours, the surface of the 5056 aluminum foil substrate which is not coated with the coating film shows obvious corrosion spots and corrosion products, while after 480 hours, the surface of the 5056 aluminum foil surface film layer which is coated with the coating film still shows no obvious corrosion signs, and after 1200 hours, the surface of the 5056 aluminum foil surface which is further coated with the silane sealing agent has no obvious corrosion signs, so that the coating film and the 5056 aluminum foil which is coated with the silane sealing agent have very excellent corrosion resistance.
3. Contact angle test
The aluminum foils of 5056 treated in example 1, example 2, example 4 and comparative example 1 were subjected to a plurality of water contact angle tests, and the results are shown in fig. 4.
As is clear from the analysis in fig. 4, the average value of the water contact angles of the surface of the 5056 aluminum foil treated in example 1 was about 45 °, the average value of the water contact angles of the surface of the 5056 aluminum foil treated in example 2 was about 33 °, good hydrophilic properties were exhibited, the average value of the water contact angles of the surface of the 5056 aluminum foil treated in example 4 was about 65 °, and the average value of the water contact angles of the surface of the 5056 aluminum foil treated in comparative example 1 was about 69 °.
4. Electrochemical polarization test
The electrochemical polarization test was performed on 5056 aluminum foil which was not coated and 5056 aluminum foils treated in examples 1 to 3, and the results are shown in fig. 5.
From the analysis in FIG. 5, it is seen that the self-corrosion potential of the 5056 aluminum foil treated in example 1 was-0.84V in 3.5% NaCl solution, which is 0.42V higher than that of the 5056 aluminum foil substrate which is not coated with the film; the self-etching current density of 5056 aluminum foil treated in example 2 was less than 10 -6 Acm -2 The self-corrosion potential of the aluminum foil is-0.86V, which is obviously higher than that of a 5056 aluminum foil substrate without coating, and is improved by 0.4V compared with that of the aluminum foil substrate 5056 without coating; the self-etching current density of 5056 aluminum foil treated in example 3 was less than 10 -6 Acm -2 Is obviously higher than that of a 5056 aluminum foil substrate which is not coated with a film, and the self-corrosion potential of the aluminum foil substrate is-0.90V, which is improved by 0.36V compared with that of the 5056 aluminum foil substrate which is not coated with the film.
5. Potassium dichromate drop test
The aluminum foil 5056 which was not coated and the aluminum foils 5056 treated in example 1, example 4 to example 6 and comparative example 1 were subjected to a potassium dichromate drop test at 25℃and the results are shown in FIGS. 6 and 7.
From the analysis in fig. 6 and 7, it is known that the aluminum foil 5056 treated in examples 1 and 5 can resist the potassium dichromate titration test for 3min, the aluminum foil 5056 treated in example 6 can resist the potassium dichromate titration test for 60s, the potassium dichromate titration resistance after silane sealing treatment in example 4 is prolonged to 13 min, and the aluminum foil 5056 without coating can only resist the potassium dichromate titration test for 30s, so that the corrosion resistance of the aluminum foil 5056 after coating and silane sealing agent sealing treatment is obviously improved.
According to the aluminum alloy surface treatment method, the aluminum alloy is placed in the hydrophilic chemical conversion film forming liquid at a lower temperature of 20-60 ℃ for a shorter time of 60-600 s under the atmospheric environment condition, so that a layer of chemical conversion film with a water contact angle smaller than 50 ℃ and a thickness of 50-150 nm can be formed on the surface of the aluminum alloy in a conversion mode, good adsorption performance is shown, and good preconditions are provided for the subsequent adsorption of an organic sealing agent. Experimental study proves that the aluminum alloy with the chemical conversion film formed on the surface can resist 480 hours of neutral salt spray test, further, after the organic sealing treatment is carried out on the aluminum alloy with the chemical conversion film formed on the surface, the neutral salt spray test is prolonged to 1200 hours, the excellent corrosion resistance is shown, the self-corrosion current is obviously improved by orders of magnitude compared with that of a matrix, and therefore, the corrosion resistance of the aluminum alloy is effectively improved.
The above embodiments are merely preferred embodiments for fully explaining the present invention, and the scope of the present invention is not limited thereto. Equivalent substitutions and modifications will occur to those skilled in the art based on the present invention, and are intended to be within the scope of the present invention.
Claims (8)
1. The aluminum alloy surface treatment method is characterized by comprising the following steps of:
s1, pretreatment: removing impurities from the surface of the aluminum alloy;
s2, coating: adjusting the pH value of the hydrophilic chemical conversion film-forming liquid to be acidic, and then placing the aluminum alloy into the acidic hydrophilic chemical conversion film-forming liquid for chemical conversion treatment so as to form a hydrophilic chemical conversion film on the surface of the aluminum alloy;
hydrophilic chemical conversion film forming liquid comprising trivalent chromium salt, fluorozirconate, organic complexing agent, additive and water;
the organic complexing agent is one or more of polyvinyl alcohol, polyethylene glycol and polyacrylamide;
the additive is fluotitanic acid and/or fluotitanate;
s3, natural aging: cleaning the coated aluminum alloy, and naturally aging in a normal temperature environment;
in the step S1, the pretreatment comprises the steps of sequentially degreasing, alkaline washing, acid washing and rinsing the aluminum alloy;
the degreasing is carried out by adopting a degreasing cleaning agent for cleaning, the cleaning temperature is 50-60 ℃, and the cleaning time is 30-120 seconds; the alkali washing is carried out by adopting 5-10 wt.% of sodium hydroxide solution, the alkali washing temperature is 30-40 ℃, and the alkali washing time is 10-60 seconds; the pickling is carried out by adopting 30-40 vol.% nitric acid solution, the pickling temperature is 20-30 ℃, and the pickling time is 10-60 seconds; the rinsing is carried out by adopting deionized water, the rinsing temperature is 70-80 ℃, and the rinsing time is 10-60 seconds;
the thickness of the chemical conversion film formed on the surface of the aluminum alloy is 50 nm-150 nm.
2. The aluminum alloy surface treatment method according to claim 1, wherein the trivalent chromium salt includes one or more of chromium sulfate, chromium nitrate, and chromium chloride.
3. The aluminum alloy surface treatment method according to claim 1, wherein the fluorozirconate includes one or both of potassium fluorozirconate and sodium fluorozirconate.
4. The method of claim 1, wherein the fluorotitanate is potassium fluorotitanate.
5. The aluminum alloy surface treatment method according to claim 1, wherein the concentration of trivalent chromium salt is 0.5-5 g/L, the concentration of fluorozirconate is 1-10 g/L, the concentration of organic complexing agent is 2-10 g/L, and the concentration of additive is 0.5-5 g/L.
6. The method for treating the surface of the aluminum alloy according to claim 1, further comprising an organic sealing treatment after natural aging, specifically: and sealing the naturally aged aluminum alloy in an organic sealing agent.
7. The method for treating an aluminum alloy surface according to claim 1, wherein in S2, the chemical conversion treatment is performed at a temperature of 20 ℃ to 60 ℃ for a time of 60 to 600 seconds.
8. The method for treating an aluminum alloy surface according to claim 6, wherein in S3, the natural aging time is 48 to 120 hours;
the organic blocking agent is a silane blocking agent.
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