CN102392284B - One-step treatment method for coloring and sealing aluminium anodic oxide film - Google Patents
One-step treatment method for coloring and sealing aluminium anodic oxide film Download PDFInfo
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- CN102392284B CN102392284B CN2011103436517A CN201110343651A CN102392284B CN 102392284 B CN102392284 B CN 102392284B CN 2011103436517 A CN2011103436517 A CN 2011103436517A CN 201110343651 A CN201110343651 A CN 201110343651A CN 102392284 B CN102392284 B CN 102392284B
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Abstract
The invention belongs to the field of metal finishing and provides a one-step treatment method for coloring and sealing an aluminium anodic oxide film. Firstly, preparing a coloring and sealing treatment fluid: adding nickel salt, fluoride, fluotitanic acid, hexamethylene tetramine, a complexing agent and a pruina restrainer into deionized water, enabling every component to reach a certain concentration, then adjusting the pH value within 5 to 6, and finally adding an organic addition agent. Secondly, implementing the one-step treatment method for coloring and sealing the aluminium anodic oxide film: washing an anodized aluminium alloy sample, then placing the sample in the treatment fluid of 20 to 40 DEG C to be treated for 5 to 25 minutes; and after the treatment, placing the sample in water of 55 to 60 DEG C for heat preservation for 5 to 15 minutes, and then washing and blow-drying the sample. Through the adoption of the method, the treatment technology is simple, chromium is avoided, the sealing treatment temperature is low, the aluminium anodic oxide film colored and sealed by the method has favorable corrosion resistance and good stain resistance and appears evenly and densely chartreuse, and coloring and sealing are finished at one step. Therefore, the method can replace the conventional chromate sealing technology.
Description
Technical field
The invention belongs to field of metal surface treatment, is a kind of Colored single stage method treatment process of aluminum anodized film, can be used as the alternative techniques of aluminum anodized film chromic salt sealing.
Background technology
Anodic oxidation is aluminium surface-treated major way, yet the vesicular structure of anode oxide film seriously affects its corrosion resistance nature, therefore must carry out suitable sealing treatment.Industrial enclosure method commonly used at present is the chromic salt sealing or take nickelous fluoride as main enclosure method, adopt the former to process and can obtain the oyster closing membrane, have good erosion resistance, yet chromic salt is highly toxic substance, the chromic salt treatment process urgently replaces; The latter is normal low temperature Chrome-free sealing treatment, commercial application at present, but this enclosure method simultaneously the antianode oxide film carry out paintedly, if need paintedly, chemical staining or electrolytic colouring technology step need to be set separately.
As patent 200810120737 discloses the enclosure method that a kind of nickelous fluoride is main component, compare the chromic salt system, the method has that technique is simple, treatment temp is low, pollute the advantages such as little.200810048493 of patents disclose water-soluble closed dose that a kind of salt by basic metal or alkaline-earth metal, complexing agent, pH buffer reagent form, have effectively replaced poisonous chromium ion.Patent 200610065870 discloses a kind of enclosure method based on Ce-Mo salt.Although above method has reached the requirement of Chrome-free sealing treatment, but the anode oxide film than the chromic salt sealing all also has a certain distance on erosion resistance, and can't obtain coloured closing membrane, if must carry out the processing step of electrolytic coloring or chemical staining before the painted anodic oxidation membrane closure of needs, increase the production cycle, reduced production efficiency.
Summary of the invention
The technical problem to be solved in the present invention is, for the deficiencies in the prior art part, a kind of method that aluminum anodized film Colored one step is processed is proposed, the method is not containing chromic salt, treatment temp is low, anode oxidation membrane corrosion resistance and good and approach the yellow-green colour color of chromic salt closing membrane after sealing, can be used as the substitution technique of chromic salt sealing.
For achieving the above object, technical scheme of the present invention is:
The treatment solution that a kind of aluminum anodized film Colored one step is processed, contain in its every premium on currency solution:
Described nickel salt is one or more in single nickel salt, nickelous fluoride, nickel acetate and nickelous carbonate;
Described fluorochemical is one or more in Sodium Fluoride, Neutral ammonium fluoride, Potassium monofluoride, fluoroboric acid and nickelous fluoride;
Prepared by described organic additive: multi-hydroxy carboxy acid, alkyl polyols, catalyzer and organic solvent are reacted 1 hour～3 hours at 100 ℃～130 ℃ in accordance with the following methods, then be cooled to room temperature, remove upper strata liquid and obtain the water-soluble organic additive of reddish-brown after its layering; Wherein the consumption of each component is: alkyl polyols and multi-hydroxy carboxy acid's mol ratio is 6～2: 1,0.2wt%～0.5wt% that the consumption of catalyzer is alcohol and sour total amount, 10wt%～50wt% that consumption of organic solvent is alcohol and sour total amount;
Described complexing agent is one or more in trolamine, amine triacetic acid, ethylenediamine tetraacetic acid (EDTA) and sulfamate;
Described pollen inhibitor is one or more in thiocarbamide, N.F,USP MANNITOL, polyoxyethylene glycol, acetic acid, p-aminophenol and glycerine.
In above-mentioned organic additive, described multi-hydroxy carboxy acid is one or more in tannic acid, gallic acid and xitix;
Described alkyl polyols is one or more in following polyvalent alcohol: ethylene glycol, 1, the 2-propylene glycol, 1, ammediol, 1, the 4-butyleneglycol, 1, the 2-butyleneglycol, 1, the 3-butyleneglycol, the 2-methyl isophthalic acid, ammediol, 2, 2-dimethyl-1, ammediol, 1, the 5-pentanediol, 1, the 6-hexylene glycol, the 3-methyl isophthalic acid, the 5-pentanediol, 2-ethyl-2-butyl 1, ammediol, 2, 2, 4-trimethylammonium-1, the 3-pentanediol, 2, 4-diethyl-1, the 5-pentanediol, the 1-methyl isophthalic acid, the 8-ethohexadiol, the 3-methyl isophthalic acid, the 6-hexylene glycol, 4-methyl 1, the 7-heptanediol, 4-propyl group 1, the 8-ethohexadiol, 1, the 9-nonanediol, sorbyl alcohol, tetramethylolmethane and Tetraglycol 99,
Described organic solvent is one or more of toluene, dimethylbenzene, chlorobenzene, N-BUTYL ACETATE, ethylene glycol monomethyl ether, propandiol butyl ether;
Described catalyzer be following acid catalyst in any one: p-methyl benzenesulfonic acid, Mono-n-butyltin, Dibutyltin oxide, dibutyl tin dilaurate, dibutyl tin acetate or monobutyl-tin-trichloride.
Wherein, alkyl polyols described in organic additive and multi-hydroxy carboxy acid's mol ratio is preferably 4: 1; The consumption of described catalyzer is preferably the 0.3wt% of alcohol and sour total amount; The consumption of described organic solvent is preferably the 38wt% of alcohol and sour total amount.Temperature of reaction prepared by described organic additive is preferably 130 ℃, and the reaction times is preferably 2 hours.
The compound method of the treatment solution that above-mentioned aluminum anodized film Colored one step is processed is: add nickel salt, fluorochemical, hydrofluotitanic acid, hexamethylenetetramine, complexing agent and pollen inhibitor in deionized water, make the concentration of each composition as mentioned above, then with nitric acid or ammoniacal liquor, treatment solution being adjusted to the pH value is 5～6, and adds appropriate pH buffer reagent boric acid; Add above-mentioned organic additive after it is stable, gets final product.
The method that a kind of aluminum anodized film Colored one step is processed: anodised aluminum alloy specimen is after washing from the beginning or deionization washing, and the treatment solution that is placed in temperature and is one of the claim 1～5 of 20 ℃～40 ℃ is processed 5 minutes～25 minutes; After processing, test piece is placed in to 55 ℃～60 ℃ water insulations 5 minutes～15 minutes, then with washed with de-ionized water, cold wind dries up and gets final product.
The preferably treatment process is: anodised aluminum alloy specimen is after washing or deionization washing from the beginning, and the treatment solution of one of claim 1～5 that to be placed in temperature be 25 ℃ is processed 10 minutes; After processing, test piece is placed in to 55 ℃ of water insulations 15 minutes, then with washed with de-ionized water, cold wind dries up and gets final product.
Below the present invention will be further explained:
The related detecting method of antianode oxidation sealing rete of the present invention comprises:
1. adopt digital camera to observe alumilite process test piece outward appearance and the color of processing through Colored of the present invention.
2. the anode oxide film surface microstructure that adopts the Japanese PHILIPS XL-30 of company type scanning electron microscope (SEM) to observe not sealing, seal with chromic salt sealing and the present invention.
3. adopt the sealing effect of phosphorus-chromium test determination anode oxide film: with reference to ISO 3210-1983 standard (being equal to GB/T8753-2005) method, preparation H
3pO
4(85%) 35ml/L, CrO
3the chromium of 20g/L-phosphoric acid corrosion liquid.By the alumilite process test piece of 2.5cm * 7cm size after deionized water is cleaned, cold wind dries up, to adopt Colored one step process of the present invention to carry out placing aging 24 hours after sealing treatment through anodised test piece, then the above-mentioned chromium-phosphoric acid corrosion liquid of putting into temperature and be 38 ℃ soaks 15 minutes, test piece weight before and after the weighing corrosion, obtain test piece weight loss Δ W, and weight loss is less, sealing effect is better, and weight loss Δ W is less than 30mg/dm
2it is qualified to be considered as, if be less than 20mg/dm
2sealing effect is good.
With chromic salt closed system and nickelous fluoride closed system, compare, main advantage of the present invention is:
(1) alumilite process Colored one trip technique of the present invention has and the similar corrosion resistance nature of chromic salt sealing treatment and yellow-green colour color, but the present invention does not contain the chromium that environment is had to severe contamination, is conducive to environment protection;
(2) anode oxide film of common nickelous fluoride sealing is colourless, and can obtain the yellow-green colour closing membrane after Colored agent of the present invention is processed, and realizes that enclosed coloring one step completes, and has certain decoration and good protective value;
(3) because the present invention has realized Colored one step after the alumilite process, process, so technical process is simple, cost is low, and this treatment process can be processed at normal temperature, is conducive to industrial applications, alternative chromic salt closing process.
The accompanying drawing explanation:
Fig. 1 is that from left to right, nickel ion concentration increases successively, color burn through the inventive method sealing gained aluminium alloy anode oxide film digital photograph;
Fig. 2 is the scanning electron microscope sem figure (2000 times) without the aluminum anodized film of sealing;
Fig. 3 is the scanning electron microscope sem figure (2000 times) of the aluminum anodized film after Colored one step of the present invention is processed;
Fig. 4 is the scanning electron microscope sem figure (2000 times) of the aluminum anodized film after the sealing of traditional chromium hydrochlorate.
Embodiment
Below in conjunction with embodiment, the present invention will be further explained, but the invention is not restricted to the scope of embodiment.
Embodiment 1:
The preparation of organic additive 1: by 25g xitix, 50g ethylene glycol, 0.2g tosic acid, and 10g dimethylbenzene joins in the four-hole round-bottomed flask with agitator arm, condensing works and division box, temperature is risen to 130 ℃ while stirring, after being incubated half an hour, add 18g dimethylbenzene, insulation, when in water trap, the amount of water no longer changes, stopped reaction.Material is down to room temperature, removes after its layering after supernatant liquid is solvent that to obtain the water miscible organic additive of reddish-brown stand-by.
Embodiment 2:
Take single nickel salt 9g, Sodium Fluoride 3g, hydrofluotitanic acid 0.5g, hexamethylenetetramine 0.6g, trolamine 1.6g, N.F,USP MANNITOL 0.8g, boric acid 1.2g, by its respectively water after dissolving, add in the large beaker of 1 liter, then add the organic additive of 0.75g embodiment 1 preparation, add deionized water to regulate pH value to 5, finally add water until one liter of solution is the Colored treatment solution.
Prepare 2024 aluminium alloy test pieces, preparation 180g/L H
2the SO4 anodizing solution, the aluminium test piece is after commercially available acid degreasing agent is processed 5 minutes, and washing, then with 1A/dm
2under current density, sulphuric acid anodizing 40min, clean with deionized water rinsing, immerses in the Colored liquid that the above-mentioned temperature prepared is 25 ℃ 15 minutes.After the test piece washing, test piece is placed in to 55 ℃ of warm water insulations 15 minutes, the oxide film after sealing is yellow-green colour, and chromium-phosphoric acid test piece weightlessness is less than 20mg/dm
2.
The experimental result determination and analysis:
(1) to the alumilite process test piece outward appearance after embodiment 2 sealing treatment as shown in Figure 1, by aluminum anodized film Colored one step treatment solution of the present invention, processed, can obtain the yellow-green colour alumilite process Colored film of even compact, color is similar to the anode oxide film outward appearance of chromic salt sealing, have ornamentally preferably, the test of phosphorus-chromium shows that closing membrane has excellent corrosion-resistant and anti-fouling performance.Therefore the ratio of the shade of anode oxidation coloration closing membrane of the present invention and each composition of encapsulant has certain relation, particularly organic additive and nickel ion content, adjustable colors as required.This anode oxidation coloration sealing one step process not only quality but also the reason that plays sealing process is speculated as: the present invention due to titanium ion in the hydrofluotitanic acid added with have containing of certain molecular weight polyhydric organic additive and aluminium substrate be combined the organic fast eolor base of formation group, in closed process, follow nickel ion and fluorion to enter in the hole of oxide film, carrying out along with sealing, form the precipitations such as aluminum fluoride, nickel hydroxide in hole, with aluminium, in conjunction with the organic colour developing group formed, also be fixed in micropore thereupon, thus the yellow-green colour color of formation even compact.
(2) scanning electron microscope (2000 times) SEM without the anode oxide film sealed schemes as Fig. 2, has shown the vesicular structure after the alumilite process; SEM as shown in Figure 3 and Figure 4 for the scanning electron microscope (2000 times) of through anode oxide film and process the inventive method of peroxychromate sealing, sealing the gained aluminum anodized film, two kinds of sealing methods all have sealing effect preferably, it is evenly smooth that the visible the inventive method of Fig. 4 is processed rear gained Colored membrane superficial tissue, and the hole in oxide film all is closed.More smooth evenly than chromic salt sealing method.
(3) through treatment solution of the present invention process respectively the anode oxide film after 10 minutes, 20 minutes and 35 minutes chromium-the weightless result of phosphoric acid corrosion is 18.76mg/dm
2, 16.84mg/dm
2and 15.31mg/dm
2, according to ISO 3210 standard codes, weight loss Δ W<30mg/dm
2it is qualified to be considered as, Δ W<20mg/dm
2be considered as sealing effect good.Therefore the anode oxide film of processing through Colored one step of the present invention reaches the erosion resistance requirement fully, and result shows, increase limited to erosion resistance long off-period.
(4) the immersion test result of anode oxide film test piece in 3.5%NaCl solution that adopts respectively chromic salt sealing and Colored agent of the present invention to obtain is as table 1.Result shows, sealing treatment agent of the present invention is equivalent to chromic salt sealing level, and the salt water resistance performance is more excellent.
Table 1 is tested in the 3.5%NaCl solution soaking through the anode oxide film of sealing treatment
Embodiment 3:
Take single nickel salt 8.5g, fluoroboric acid 5.5, hydrofluotitanic acid 0.5g, hexamethylenetetramine 0.6g, sodium ethylene diamine tetracetate 0.5g, thiocarbamide 0.8g, boric acid 1.5g, add after its water is dissolved in the large beaker of 1 liter, then adds the organic additive 0.8g of embodiment 1, stir and regulate pH to 6, add water to 1 liter and be the Colored treatment solution.
Prepare 2024 aluminium alloy test pieces, the anodizing solution of preparation sulfuric acid (98%) 180g/L, the aluminium test piece is after alkaline defatting agent is processed 5 minutes, and washing, then after nitric acid polishing in 1: 1 washing, with 1A/dm
2under current density, sulphuric acid anodizing is 20 minutes, clean with deionized water rinsing, immerses in the Colored liquid that the above-mentioned temperature prepared is 25 ℃ 15 minutes.After the test piece washing, test piece is placed in to 55 ℃ of warm water insulations 15 minutes, it is yellow that the oxide film after sealing is, and chromium-phosphoric acid weightlessness is less than 20mg/dm
2.
Embodiment 4:
The preparation of organic additive: by 26g gallic acid, 48g 1,4-butyleneglycol, 0.2g dibutyl tin dilaurate, and the 12g N-BUTYL ACETATE joins in the four-hole round-bottomed flask with agitator arm, condensation and division box, temperature is risen to 120 ℃ while stirring, after being incubated half an hour, add the 16g N-BUTYL ACETATE, insulation, when in water trap, the amount of water no longer changes, stopped reaction.Material is down to room temperature, and removing supernatant liquid after its layering, to obtain brown organic additive stand-by.
Embodiment 5:
Take nickel acetate 10.5g, Potassium monofluoride 7.5, hydrofluotitanic acid 0.8g, hexamethylenetetramine 0.9g, thionamic acid sodium 1.5g, polyoxyethylene glycol 0.6g, boric acid 0.8g, add after its water is dissolved in the large beaker of 1 liter, then add the organic additive 1.0g of embodiment 4, stir and test and regulate the pH value and add water to one liter 5 and be the Colored treatment solution.
The test piece of preparation pure aluminum foil, preparation 160g/LH
2sO
4and 80g/LH
3pO
4mixed acid anodic oxidation liquid, the aluminium test piece is after commercially available acid degreasing agent is processed 5 minutes, and washing, then with 1A/dm
2under current density, sulphuric acid anodizing is 20 minutes, clean with deionized water rinsing, immerses in the Colored liquid that the above-mentioned temperature prepared is 25 ℃ 15 minutes.After the test piece washing, test piece is placed in to 55 ℃ of warm water insulations 15 minutes, it is yellow that the oxide film after sealing is, and chromium-phosphoric acid weightlessness is less than 20mg/dm
2.
Embodiment 6:
Take single nickel salt 12.5g, fluoride amine 6.5, hydrofluotitanic acid 0.7g, hexamethylenetetramine 0.6g, sodium ethylene diamine tetracetate 2.5g, p-aminophenol 0.6g, boric acid 1.3g, add after its water is dissolved in the large beaker of 1 liter, then adds the organic additive of 0.9g embodiment 4, stir and regulate pH value to 5.5, add water to one liter and be the Colored treatment solution.
Prepare 6061 aluminium alloy test plate (panel)s, preparation 180g/L sulphuric acid anodizing liquid, the aluminium test piece is after commercially available acid degreasing agent is processed 5 minutes, and washing, then with 1A/dm
2under current density, sulphuric acid anodizing is 20 minutes, clean with deionized water rinsing, immerses in the Colored liquid that the above-mentioned temperature prepared is 25 ℃ 10 minutes.After the test piece washing, test piece is placed in to 55 ℃ of warm water insulations 15 minutes, the oxide film after sealing is oyster, and chromium-phosphoric acid test piece weightlessness is less than 20mg/dm
2.
Claims (7)
1. the treatment solution that aluminum anodized film Colored one step is processed, is characterized in that, in its every premium on currency solution, contains:
Described nickel salt is one or more in single nickel salt, nickel acetate and nickelous carbonate;
Described fluorochemical is one or more in Sodium Fluoride, Neutral ammonium fluoride, Potassium monofluoride, fluoroboric acid and nickelous fluoride;
Prepared by described organic additive: multi-hydroxy carboxy acid, alkyl polyols, catalyzer and organic solvent are reacted 1 hour～3 hours at 110 ℃～140 ℃ in accordance with the following methods, then be cooled to room temperature, remove upper strata liquid and obtain the reddish-brown organic additive after its layering; Wherein the consumption of each component is: alkyl polyols and multi-hydroxy carboxy acid's mol ratio is 6～2 ︰ 1,0.2wt%～0.5wt% that the consumption of catalyzer is alcohol and sour total amount, 10wt%～50wt% that consumption of organic solvent is alcohol and sour total amount;
Described complexing agent is one or more in trolamine, amine triacetic acid, ethylenediamine tetraacetic acid (EDTA) and sulfamate;
Described pollen inhibitor is one or more in thiocarbamide, N.F,USP MANNITOL, polyoxyethylene glycol, acetic acid, p-aminophenol and glycerine.
2. the treatment solution that a kind of aluminum anodized film Colored one step is processed according to claim 1 is characterized in that multi-hydroxy carboxy acid described in organic additive is one or more in tannic acid, gallic acid and xitix;
Described alkyl polyols is one or more in following polyvalent alcohol: ethylene glycol, 1, the 2-propylene glycol, 1, ammediol, 1, the 4-butyleneglycol, 1, the 2-butyleneglycol, 1, the 3-butyleneglycol, the 2-methyl isophthalic acid, ammediol, 2, 2-dimethyl-1, ammediol, 1, the 5-pentanediol, 1, the 6-hexylene glycol, the 3-methyl isophthalic acid, the 5-pentanediol, 2-ethyl-2-butyl 1, ammediol, 2, 2, 4-trimethylammonium-1, the 3-pentanediol, 2, 4-diethyl-1, the 5-pentanediol, the 1-methyl isophthalic acid, the 8-ethohexadiol, the 3-methyl isophthalic acid, the 6-hexylene glycol, 4-methyl 1, the 7-heptanediol, 4-propyl group 1, the 8-ethohexadiol, 1, the 9-nonanediol, sorbyl alcohol, tetramethylolmethane and Tetraglycol 99,
Described organic solvent is one or more of toluene, dimethylbenzene, chlorobenzene, N-BUTYL ACETATE, ethylene glycol monomethyl ether, propandiol butyl ether;
Described catalyzer be following acid catalyst in any one: p-methyl benzenesulfonic acid, Mono-n-butyltin, Dibutyltin oxide, dibutyl tin dilaurate, dibutyl tin acetate or monobutyl-tin-trichloride.
3. the treatment solution that a kind of aluminum anodized film Colored one step is processed according to claim 1 is characterized in that alkyl polyols described in organic additive and multi-hydroxy carboxy acid's mol ratio is 4 ︰ 1; The 0.3wt% that the consumption of described catalyzer is alcohol and sour total amount; The 38wt% that the consumption of described organic solvent is alcohol and sour total amount.
4. the treatment solution that a kind of aluminum anodized film Colored one step is processed according to claim 1 is characterized in that temperature of reaction prepared by described organic additive is 130 ℃, and the reaction times is 2 hours.
5. the treatment solution that a kind of aluminum anodized film Colored one step is processed according to claim 1, it is characterized in that, compound method is: add nickel salt, fluorochemical, hydrofluotitanic acid, hexamethylenetetramine, complexing agent and pollen inhibitor in deionized water, the concentration that makes each composition is the concentration described in claim 1, then with nitric acid or ammoniacal liquor, treatment solution being adjusted to the pH value is 5～6, and adds appropriate pH buffer reagent boric acid; Add above-mentioned organic additive after it is stable, gets final product.
6. the method that an aluminum anodized film Colored one step is processed, it is characterized in that, anodised aluminum alloy specimen is after washing or deionization washing from the beginning, and the treatment solution that is placed in temperature and is one of the claim 1-5 of 20 ℃～40 ℃ is processed 5 minutes～25 minutes; After processing, test piece is placed in to 55 ℃～60 ℃ water insulations 5 minutes～15 minutes, then with washed with de-ionized water, cold wind dries up and gets final product.
7. a kind of method that aluminum anodized film Colored one step is processed according to claim 6, it is characterized in that, anodised aluminum alloy specimen is after washing or deionization washing from the beginning, and the treatment solution of one of claim 1～5 that to be placed in temperature be 25 ℃ is processed 10 minutes; After processing, test piece is placed in to 55 ℃ of water insulations 15 minutes, then with washed with de-ionized water, cold wind dries up and gets final product.
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| CN105063716B (en) * | 2015-08-12 | 2017-06-13 | 浙江苏泊尔股份有限公司 | A kind of horniness anode oxide film enclosure method for improving alkali resistance |
| CN105200495A (en) * | 2015-09-24 | 2015-12-30 | 马鞍山杰创塑胶科技有限公司 | Nickel-free hole sealing agent for improving compactness of aluminum alloy anode oxide film and preparation method of nickel-free hole sealing agent |
| CN105200484A (en) * | 2015-09-24 | 2015-12-30 | 马鞍山杰创塑胶科技有限公司 | Aluminum alloy anodic oxide film nickel-free sealant for harsh environment and preparation method thereof |
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| CN109554740A (en) * | 2018-11-29 | 2019-04-02 | 广州国弘化学有限公司 | A kind of aluminium alloy sealer and preparation method thereof |
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| CN109913926B (en) * | 2019-04-17 | 2020-06-26 | 安徽华淮新材料有限公司 | Aluminum alloy anodic oxide film sealant and sealing method thereof |
| CN113279035A (en) * | 2021-05-15 | 2021-08-20 | 江门市优博科技有限公司 | Novel sealing agent for aluminum and aluminum alloy anodic oxide film and preparation method thereof |
| CN114059129B (en) * | 2021-11-24 | 2023-04-14 | 武汉风帆电化科技股份有限公司 | Color fixing agent for aluminum and aluminum alloy after anodic oxide film dyeing and preparation method |
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