CN117845306A - Hole sealing technology for improving alkali resistance of dyed aluminum alloy anodic oxide film - Google Patents
Hole sealing technology for improving alkali resistance of dyed aluminum alloy anodic oxide film Download PDFInfo
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- CN117845306A CN117845306A CN202410259005.XA CN202410259005A CN117845306A CN 117845306 A CN117845306 A CN 117845306A CN 202410259005 A CN202410259005 A CN 202410259005A CN 117845306 A CN117845306 A CN 117845306A
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- aluminum alloy
- oxide film
- hole sealing
- alkali resistance
- alloy workpiece
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- 229910000838 Al alloy Inorganic materials 0.000 title claims abstract description 106
- 238000007789 sealing Methods 0.000 title claims abstract description 85
- 239000003513 alkali Substances 0.000 title claims abstract description 44
- 239000010407 anodic oxide Substances 0.000 title claims abstract description 21
- 238000005516 engineering process Methods 0.000 title description 3
- 238000004043 dyeing Methods 0.000 claims abstract description 33
- 230000003647 oxidation Effects 0.000 claims abstract description 32
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 26
- 230000008569 process Effects 0.000 claims abstract description 22
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 22
- 230000007797 corrosion Effects 0.000 claims description 9
- 238000005260 corrosion Methods 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 239000003112 inhibitor Substances 0.000 claims description 5
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- BDKLKNJTMLIAFE-UHFFFAOYSA-N 2-(3-fluorophenyl)-1,3-oxazole-4-carbaldehyde Chemical compound FC1=CC=CC(C=2OC=C(C=O)N=2)=C1 BDKLKNJTMLIAFE-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 claims description 2
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 229940087562 sodium acetate trihydrate Drugs 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- 239000003086 colorant Substances 0.000 abstract description 6
- 239000000243 solution Substances 0.000 description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 239000000126 substance Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000007670 refining Methods 0.000 description 7
- 238000002791 soaking Methods 0.000 description 6
- 239000012459 cleaning agent Substances 0.000 description 5
- 238000005238 degreasing Methods 0.000 description 5
- 239000000975 dye Substances 0.000 description 5
- 238000005498 polishing Methods 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 244000181980 Fraxinus excelsior Species 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005538 encapsulation Methods 0.000 description 3
- 238000007689 inspection Methods 0.000 description 3
- 229920001661 Chitosan Polymers 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- PZNOBXVHZYGUEX-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine;hydrochloride Chemical compound Cl.C=CCNCC=C PZNOBXVHZYGUEX-UHFFFAOYSA-N 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 239000001045 blue dye Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- FEWJPZIEWOKRBE-LWMBPPNESA-N levotartaric acid Chemical compound OC(=O)[C@@H](O)[C@H](O)C(O)=O FEWJPZIEWOKRBE-LWMBPPNESA-N 0.000 description 1
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 1
- 229910052912 lithium silicate Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000001044 red dye Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000176 sodium gluconate Substances 0.000 description 1
- 235000012207 sodium gluconate Nutrition 0.000 description 1
- 229940005574 sodium gluconate Drugs 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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- 230000000007 visual effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Chemical Treatment Of Metals (AREA)
Abstract
The invention discloses a hole sealing process for improving alkali resistance of a dyed aluminum alloy anodic oxide film, which comprises the following steps of: s1: pre-treating an aluminum alloy workpiece; s2: placing the aluminum alloy workpiece treated in the step S1 into an oxidation tank liquid for anodic oxidation, and forming an oxidation film on the surface of the aluminum alloy workpiece; s3: dyeing the aluminum alloy workpiece; s4: placing an aluminum alloy workpiece in a pre-sealed groove liquid for fixation; s5: placing an aluminum alloy workpiece in the pre-sealed two-tank solution to fill the intermediate layer of the oxide film; s6: and carrying out hole sealing treatment on the aluminum alloy workpiece. The invention can lead the dyed aluminum alloy oxide film to have rich colors and higher alkali resistance, and meet the harsh alkali resistance requirement of the new energy automobile field on aluminum alloy parts.
Description
Technical Field
The invention relates to the technical field of surface treatment of aluminum alloy parts of new energy automobiles, in particular to a hole sealing process for improving alkali resistance of a dyed aluminum alloy anodic oxide film.
Background
The density of the aluminum alloy material is 2.7g/cm 3 About, the density of the iron and steel material is 7.8g/cm 3 About, the density of the aluminum alloy material is only approximately one third of that of the steel material. In the field of new energy automobiles, the application of aluminum alloy is becoming wider and wider. The aluminum alloy used for the new energy automobile body or the parts has the advantages that:
1. the aluminum alloy has low density and light weight, so that the new energy automobile is light and the energy efficiency is improved.
2. The aluminum alloy is a highly recyclable material, and the aluminum alloy vehicle body is used for reducing resource waste and promoting sustainable development.
3. The aluminum alloy has good processing plasticity and is easy to realize complex part design processing.
Most cleaning agents used in the automotive service cleaning process are relatively alkaline and have a pH of about 10.5 to 13.5. The aluminum alloy oxide film which is the most commonly used aluminum alloy surface treatment process has certain alkali corrosion resistance after hole sealing, but the aluminum alloy oxide film (the main component is aluminum oxide) is an amphoteric substance. After the parts are soaked by the alkaline cleaning agent for many times, the parts are corroded to a certain extent, so that the appearance or the function is influenced, and the improvement of the alkali resistance of the aluminum alloy oxide film is a great challenge.
In the prior art, only a few researches relate to hole sealing agents or preparation processes for improving the alkali resistance of the aluminum alloy anodic oxide film, but the improvement of the alkali resistance of the dyed aluminum alloy anodic oxide film is rarely related.
Therefore, how to improve the alkali resistance of the dyed aluminum alloy anodic oxide film is a problem to be solved.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a hole sealing process for improving alkali resistance of a dyed aluminum alloy anodic oxide film. The method is realized by the following technical scheme:
a hole sealing process for improving alkali resistance of a dyed aluminum alloy anodic oxide film comprises the following steps:
s1: pre-treating an aluminum alloy workpiece;
s2: placing the aluminum alloy workpiece treated in the step S1 into an oxidation tank liquid for anodic oxidation, and forming an oxidation film on the surface of the aluminum alloy workpiece;
s3: dyeing the aluminum alloy workpiece;
s4: placing an aluminum alloy workpiece into a pre-sealed tank liquor for fixation, wherein the pre-sealed tank liquor is FK310 with the concentration of 5-10 g/L;
s5: filling an oxide film by placing an aluminum alloy workpiece in a pre-sealed second tank solution, wherein the pre-sealed second tank solution is 10-30wt% of FK294 hole sealing agent, the temperature of the pre-sealed second tank solution is 80-98 ℃, and the time of the aluminum alloy workpiece in the pre-sealed second tank solution is 10-30min;
s6: and carrying out hole sealing treatment on the aluminum alloy workpiece.
Further, in step S2, the temperature of the oxidation bath solution is 10-30deg.C, the current density of the anodic oxidation is 0.8-2ASD (e.g. 0.8 ASD, 1.0 ASD, 1.5 ASD, 2.0 ASD), and the anodic oxidation time is 20-80min.
Further, the dyeing step in step S3 includes: placing the aluminum alloy workpiece into a dyeing tank liquor for dyeing treatment, wherein the dyeing tank liquor is organic dye, the concentration of the dyeing tank liquor is 0.5-20g/L, the dyeing treatment temperature is 15-55 ℃ and the dyeing treatment time is 0.5-20min. The organic dyes of gold, black, red, blue, etc. colors may be selected according to the desired colors. If the natural color workpiece is to be made, the dyeing step can be omitted, and the process of the invention is also suitable for making the natural color aluminum alloy workpiece.
Further, in step S1, the pretreatment step may be different combinations of degreasing, overbase, ash removal, chemical polishing, ash removal, degreasing, chemical polishing, ash removal, and the like. The main purpose is to remove grease, dirt, natural oxide skin and the like on the surface of the aluminum alloy, and endow the surface of the aluminum alloy with certain glossiness, so as to provide a clean surface for the next step of anodic oxidation.
Further, the pre-sealing tank liquor is FK310 (Shenzhen Wanjiayuan refining technology Co., ltd.) solution with the concentration of 5-10g/L, and is mainly used for fixing colors of dyed aluminum oxide workpieces. The main components of FK310 comprise 75-80% of nickel acetate tetrahydrate, 15-20% of sodium acetate trihydrate, 2-5% of a color fixing agent, 0.5-1% of an ash inhibitor and 0.2-0.5% of a surfactant, wherein the color fixing agent is polydimethyl diallyl ammonium chloride and chitosan quaternary ammonium salt (HACC-102), the mass ratio of the polydimethyl diallyl ammonium chloride to the chitosan quaternary ammonium salt is 1:1.3, the pH value of a pre-sealed groove liquid is 5.3-5.8, and glacial acetic acid or ammonia water is used for regulating the pH value.
Further, in the step S4, the fixation time of the aluminum alloy workpiece in the pre-sealed groove liquid is 0.5-3min, and the temperature is 60-70 ℃. The dyed aluminum alloy oxide film can ensure that the dye adsorbed by the oxide film layer is sealed in the oxide film holes and cannot run off through the fixation effect of pre-sealing one. The inventor of the application finds that the color fixing time is short or the color fixing temperature is too low in the first pre-sealing step, the color fixing effect is poor, and the color bleeding occurs in the second pre-sealing step; the long fixation time or the high fixation temperature can cause the oxide film to be too much closed in the first step of pre-sealing, so that the amount of filling substances entering the oxide film in the second step of pre-sealing is reduced, thereby influencing the alkali resistance of the whole oxide film.
Further, the pH value of the pre-sealed secondary tank solution is 8.5-10.0, and the pH value is adjusted by dilute glacial acetic acid or sodium hydroxide solution.
In the step S5, the temperature of the pre-sealed two-groove liquid is 80-98 ℃, and the time of the aluminum alloy workpiece in the pre-sealed two-groove liquid is 10-30min. The inventor of the application finds that when the temperature of the pre-sealing second tank liquor is too low or the time is too short, the effective substances in the pre-sealing second enter the oxide film Kong Taishao too slowly to enable the oxide film to have excellent alkali resistance; however, the temperature is too high or the time is prolonged, so that the alkali resistance of the oxide film cannot be obviously improved, and the energy consumption is increased.
Further, the FK294 hole sealing agent comprises 35-50g/L of sodium sulfate, 115-135g/L of silicate and 10-15g/L of corrosion inhibitor, wherein the sodium sulfate is preferably analytically pure anhydrous sodium sulfate, the silicate is one or more of potassium silicate, potassium sodium silicate, lithium silicate and quaternary ammonium silicate, and the corrosion inhibitor is one or more of thiourea, sodium molybdate and sodium gluconate.
Further, the hole sealing groove liquid in the step S6 is a middle-high temperature nickel-containing hole sealing agent or a nickel-free hole sealing agent, and the nickel-containing hole sealing agent or the nickel-free hole sealing agent can be purchased from the market. The hole sealing temperature is 80-98 ℃, and the hole sealing time is 20-60min. The step is to strengthen the hole sealing effect, so that the aluminum alloy oxide film layer not only has excellent alkali resistance, but also has comprehensive corrosion resistance.
In step S2, the oxidation bath solution is one of a monosulfuric acid system, a sulfuric acid-organic acid system, and an organic acid system, and a film forming auxiliary agent may be added to the above system.
Further, in step S2, the cathode plate at the time of anodic oxidation is one of an aluminum plate, a lead plate, or a carbon plate. Through the anodic oxidation process, a compact oxide film layer with a certain thickness can be formed on the surface of the aluminum alloy workpiece.
S4, dye molecules can be rapidly sealed in the oxide film holes through pre-sealing a tank liquor for a short time (0.5-3 min) fixation treatment, so that the uniformity of the appearance color of the oxide film is ensured; step S5, filling the oxide film with FK294 hole sealing agent for the second time, and forming an alkali-resistant compound with the oxide film, so that the alkali resistance of the oxide film is greatly improved; and then strengthening and supplementing the oxide film layer through the middle-high temperature hole sealing in the step S6. Through the combination of a plurality of steps, the oxide film is completely sealed, and has excellent corrosion resistance, and especially the alkali resistance is improved by more than about 5 times.
Compared with the prior art, the invention has the beneficial effects that:
1. the dyed aluminum alloy oxide film has rich colors and higher alkali resistance, and meets the severe alkali resistance requirement of the aluminum alloy parts of the new energy automobile;
2. the process of the invention does not contain elements such as chromium, fluorine and the like, is safe and environment-friendly, and has simple wastewater treatment.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The aluminum alloy workpiece materials used in the following examples were 6063 series aluminum alloy (40 x 20 x 1mm gauge)
Example 1
S1, carrying out pretreatment on an aluminum alloy workpiece:
a. degreasing: adopting a cleaning agent QX3106 (product of Huiyang Kogyo chemical industry Co., ltd., huiyou) with the concentration of 50g/L, soaking an aluminum alloy workpiece in the solution at the temperature of 55 ℃ for 5min;
b. and (3) alkali removal: immersing an aluminum alloy workpiece in a sodium hydroxide solution with the concentration of 50g/L at the temperature of 55 ℃ for 1min;
c. ash removal: immersing an aluminum alloy workpiece in a CH351 ash removal agent (product of Huiyang Kogyo chemical industry Co., ltd.) solution with the mass concentration of 15%, wherein the duration is 1min at normal temperature;
d. chemical polishing: the volume ratio of the prepared phosphoric acid to the sulfuric acid is 3:1, immersing an aluminum alloy workpiece in the chemical polishing solution at 90 ℃ for 1min;
e. ash removal: then the aluminum alloy workpiece is soaked in CH351 ash remover solution with the mass concentration of 15 percent, the temperature is normal temperature, and the duration is 1min.
And continuously carrying out the processes and washing the aluminum alloy workpiece with clean and smooth surface.
S2, anodic oxidation:
and (3) placing the aluminum alloy workpiece treated by the step (S1) into an oxidation tank liquor for anodic oxidation, wherein the oxidation tank liquor is sulfuric acid of 200g/L, the temperature is 18 ℃, a cathode plate is a carbon plate, the current density is 1.0 ASD, the anodic oxidation time is 45min, and an oxide film with the thickness of 12-15um is generated on the surface of the aluminum alloy workpiece.
S3, dyeing:
and (3) placing the aluminum alloy workpiece into a dyeing bath solution for dyeing, wherein the dyeing bath solution adopts black dye Aoshan 415 with the concentration of 10g/L, the dyeing temperature is 40 ℃, and the dyeing is carried out for 15min.
S4, pre-sealing:
and (3) placing the aluminum alloy workpiece into a pre-sealed tank liquor for fixation, wherein the pre-sealed tank liquor is FK310 (Shenzhen Wanjia refining technology Co., ltd.) with the concentration of 5g/L, the fixation temperature is 60 ℃, the fixation time is 0.5min, and the pH is 5.3.
S5, pre-sealing two:
the aluminum alloy workpiece is placed in a pre-sealed second tank liquor for filling an intermediate layer of an oxide film, wherein the pre-sealed second tank liquor is FK294 hole sealing agent (produced by Shenzhen Wanjia refining technology Co., ltd.) with the mass concentration of 10%, and the pH value of the pre-sealed second tank liquor is 8.5. The temperature of the pre-sealing two tank liquor is 80 ℃, and the time for pre-sealing two tank liquor is 10min.
S6, hole sealing:
sealing with sealing agent SH-900 (product of Bo Anmei Innovative technology (Guangzhou)), concentration of 10g/L, sealing temperature of 80deg.C, and sealing time of 20min.
Example 2
S1, carrying out pretreatment on an aluminum alloy workpiece:
a. degreasing: soaking an aluminum alloy workpiece in a cleaning agent QX3106 (product of Huiyang Kogyo chemical industry Co., ltd.) with the concentration of 50g/L at 55 ℃ for 5min;
b. and (3) alkali removal: immersing the aluminum alloy workpiece in a sodium hydroxide solution with the concentration of 50g/L at the temperature of 55 ℃ for 1min;
c. ash removal: then the aluminum alloy workpiece is soaked in a CH351 ash remover (product of Huiyang Kogyo chemical industry Co., ltd.) solution with the mass concentration of 15 percent for 1min at normal temperature.
S2, anodic oxidation:
and (3) placing the aluminum alloy workpiece treated by the method S1 into an oxidation tank liquor for anodic oxidation, wherein the oxidation tank liquor is 70g/L sulfuric acid and 60g/L tartaric acid, the temperature is 20 ℃, a cathode plate is a carbon plate, the current density is 1.0 ASD, the anodic oxidation time is 45min, and an oxide film with the thickness of 12-15um is generated on the surface of the aluminum alloy workpiece.
S3, dyeing:
and (3) placing the aluminum alloy workpiece into a dyeing bath solution for dyeing, wherein the dyeing bath solution adopts blue dye Aohe 501 with the concentration of 10g/L and the dyeing temperature of 40 ℃ for 15min.
S4, pre-sealing:
and (3) placing the aluminum alloy workpiece into a pre-sealed tank liquor for fixation, wherein the pre-sealed tank liquor is 7.5g/L FK310 (Shenzhen Wanjia refining technology Co., ltd.) and the fixation temperature is 65 ℃ for 2min and the pH value is 5.5.
S5, pre-sealing two:
and (3) placing the aluminum alloy workpiece in a pre-sealed second tank liquor to fill the intermediate layer of the oxide film, wherein the pre-sealed second tank liquor is FK294 hole sealing agent (produced by Shenzhen Wanjia refining technology Co., ltd.) with the mass concentration of 20%, and the pH value of the pre-sealed second tank liquor is 9.5. The temperature of the pre-sealing two tank liquor is 90 ℃, and the time for pre-sealing two tank liquor is 20min.
S6, hole sealing:
the nickel-free medium-high temperature hole sealing agent FK290 (product of Shenzhen Wanjiayuan refined technology Co., ltd.) is used for hole sealing treatment, the concentration is 100ml/L, the hole sealing temperature is 90 ℃, and the time is 45min.
Example 3
S1, carrying out pretreatment on an aluminum alloy workpiece:
a. degreasing: adopting a cleaning agent QX3106 (product of Huiyang Kogyo chemical industry Co., ltd., huiyou) with the concentration of 50g/L, soaking an aluminum alloy workpiece in the solution at the temperature of 55 ℃ for 5min;
b. chemical polishing: immersing the aluminum alloy workpiece into phosphoric acid and sulfuric acid with the volume ratio of 3:1, the temperature is 90 ℃ and the duration is 1min;
c. ash removal: then, soaking the aluminum alloy workpiece in a CH351 (product of Huiyang Kogyo chemical industry Co., ltd.) solution with the mass concentration of 15%, wherein the duration is 1min at normal temperature;
s2, anodic oxidation:
and (3) placing the aluminum alloy workpiece treated by the method S1 into an oxidation tank liquor for anodic oxidation, wherein the oxidation tank liquor is 40 g/L oxalic acid and 5g/L formic acid, the temperature is 30 ℃, a cathode plate is a carbon plate, the current density is 1.33ASD, the anodic oxidation time is 35min, and an oxide film with the thickness of 12-15um is generated on the surface of the aluminum alloy workpiece.
S3, dyeing:
and (3) placing the aluminum alloy workpiece in a dyeing tank liquor for dyeing treatment, wherein the dyeing tank liquor adopts red dye Aohe 102, the concentration is 10g/L, the dyeing temperature is 40 ℃, and the dyeing is carried out for 15min.
S4, pre-sealing:
and (3) placing the aluminum alloy workpiece into a pre-sealed tank liquor for fixation, wherein the pre-sealed tank liquor is FK310 (Shenzhen Wanjia refining technology Co., ltd.) with the concentration of 10g/L, the fixation temperature is 70 ℃, the fixation time is 3min, and the pH is 5.8.
S5, pre-sealing two:
the aluminum alloy workpiece is placed in a pre-sealed second tank liquor for filling an intermediate layer of an oxide film, wherein the pre-sealed second tank liquor is FK294 hole sealing agent (produced by Shenzhen Wanjia refining technology Co., ltd.) with the mass concentration of 30%, and the pH value of the pre-sealed second tank liquor is 10.0. The temperature of the pre-sealing two tank liquor is 98 ℃, and the time for pre-sealing two tank liquor is 30min.
S6, hole sealing:
and (3) carrying out hole sealing treatment by using an omnifacial hole sealing agent DX500, wherein the concentration is 10g/L, the hole sealing temperature is 98 ℃, and the time is 60 minutes.
Comparative example 1
The only difference from example 1 is that: comparative example 1 omits step S4, and the rest is the same as in example 1.
Comparative example 2
The only difference from example 1 is that: comparative example 2 omits step S5, and the rest is the same as in example 1.
Comparative example 3
The only difference from example 1 is that: comparative example 3 omits steps S4 and S5, and the rest is the same as in example 1.
Comparative example 4
The only difference from example 1 is that: comparative example 4 omits step S6, and the rest is the same as in example 1.
< appearance and Performance test >
Appearance inspection: the appearance inspection is to use a visual mode under a fluorescent lamp to see the uniformity of the overall color of the workpiece, and to take the workpiece which is only subjected to the dyeing step (namely, only subjected to the dyeing step and no dyeing subsequent treatment), and compare the workpiece with the dyed workpiece which is subjected to the dyeing step (namely, one or more steps of pre-sealing, pre-sealing and hole sealing treatment are performed after the dyeing step), wherein the phenomenon is abnormal if the appearance of the workpiece is colored and flows.
Alkali resistance test: there are two ways, test 1 and test 2, respectively;
test 1:
the aluminum alloy oxidized workpiece is soaked in 10% sodium hydroxide solution for 150 seconds without fading (under the condition of no wiping). In order to more clearly observe the appearance change of the workpiece before and after soaking, half of the workpiece is soaked in sodium hydroxide test solution during testing, and the other half is not soaked. After the test is finished, the workpiece is washed by water and dried, and whether the color change exists between the soaked part and the non-soaked part or not is observed, and whether corrosion exists or not is observed.
Test 2:
according to the 5.5.2 drop alkali test method in GB/T8013.1-2007, 10mg of sodium hydroxide solution with the concentration of 100g/L is dripped on the surface of a sample at 35+/-1 ℃, the dripping position is visually observed until corrosion bubbling is generated, and the time for an oxide film to be penetrated is recorded.
The aluminum alloy oxidized workpieces obtained in examples 1 to 3 and comparative examples 1 to 4 were subjected to the above-mentioned appearance inspection and alkali resistance tests 1 and 2, respectively, and the test results are shown in table 1.
Table 1.
Note that: in the table, "appearance OK" indicates that the appearance meets the requirements, and "appearance NG" indicates that the appearance does not meet the requirements.
As can be seen from Table 1, the hole sealing process for improving the alkali resistance of the dyed aluminum alloy anodic oxide film provided by the invention enables the dyed aluminum alloy anodic oxide film to have rich colors and higher alkali resistance by a unique two-step pre-sealing step hole sealing method, and meets the harsh alkali resistance test requirement. It can be seen from comparative example 1 that the pre-encapsulation in step S4 plays a major role in fixation.
Comparative examples 2 and 3 show that if the second pre-encapsulation is not performed, the workpiece has the phenomena of discoloration and foaming corrosion in the alkali resistance test soaking process, because the components in the second pre-encapsulation can form a compound layer with good alkali resistance with the aluminum alloy oxide film, and the alkali resistance of the aluminum alloy oxide film is improved;
comparative example 4 illustrates that the middle-high temperature hole sealing in step S6 is an enhancement and supplement to the alkali resistance of the oxide film, and the pores of the oxide film cannot be completely sealed by the first and second pre-seals alone.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (10)
1. The hole sealing process for improving alkali resistance of the dyed aluminum alloy anodic oxide film is characterized by comprising the following steps of:
s1: pre-treating an aluminum alloy workpiece;
s2: placing the aluminum alloy workpiece treated in the step S1 into an oxidation tank liquid for anodic oxidation, and forming an oxidation film on the surface of the aluminum alloy workpiece;
s3: dyeing the aluminum alloy workpiece;
s4: placing an aluminum alloy workpiece into a pre-sealed tank liquor for fixation, wherein the pre-sealed tank liquor is FK310 with the concentration of 5-10 g/L;
s5: filling an oxide film by placing an aluminum alloy workpiece in a pre-sealed second tank solution, wherein the pre-sealed second tank solution is 10-30wt% of FK294 hole sealing agent, the temperature of the pre-sealed second tank solution is 80-98 ℃, and the time of the aluminum alloy workpiece in the pre-sealed second tank solution is 10-30min;
s6: and carrying out hole sealing treatment on the aluminum alloy workpiece.
2. The hole sealing process for improving alkali resistance of the dyed aluminum alloy anodic oxide film according to claim 1, wherein in the step S4, the fixation time is 0.5-3min.
3. The hole sealing process for improving alkali resistance of the dyed aluminum alloy anodic oxide film according to claim 1, wherein in the step S4, the fixation temperature is 60-70 ℃.
4. The hole sealing process for improving alkali resistance of the dyed aluminum alloy anodic oxide film according to claim 1, wherein in the step S6, the hole sealing groove liquid is a nickel-containing hole sealing agent or a nickel-free hole sealing agent.
5. The sealing process for improving alkali resistance of a dyed aluminum alloy anodic oxide film according to claim 1, wherein in step S6, the sealing temperature is 80-98 ℃.
6. The hole sealing process for improving alkali resistance of the dyed aluminum alloy anodic oxide film according to claim 1, wherein in step S6, the hole sealing time is 20-60min.
7. The hole sealing process for improving alkali resistance of the dyed aluminum alloy anodic oxide film according to claim 1, wherein in the step S2, the oxidation bath solution is one of a monosulfuric acid system, a sulfuric acid-organic acid system or an organic acid system.
8. The hole sealing process for improving alkali resistance of the dyed aluminum alloy anodic oxide film according to claim 1, wherein the pH value of the pre-sealing two-tank solution is 8.5-10.0.
9. The hole sealing process for improving alkali resistance of a dyed aluminum alloy anodic oxide film according to claim 1, wherein the FK310 comprises 75-80wt% nickel acetate tetrahydrate, 15-20wt% sodium acetate trihydrate, 2-5wt% fixing agent, 0.5-1wt% ash inhibitor and 0.2-0.5wt% surfactant.
10. The hole sealing process for improving alkali resistance of the dyed aluminum alloy anodic oxide film according to claim 1, wherein the components of the FK294 hole sealing agent comprise 35-50g/L sodium sulfate, 115-135g/L silicate and 10-15g/L corrosion inhibitor.
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