CN104894552A - Method for forming golden yellow film on surface of aluminum alloy - Google Patents
Method for forming golden yellow film on surface of aluminum alloy Download PDFInfo
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- CN104894552A CN104894552A CN201510342484.2A CN201510342484A CN104894552A CN 104894552 A CN104894552 A CN 104894552A CN 201510342484 A CN201510342484 A CN 201510342484A CN 104894552 A CN104894552 A CN 104894552A
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- aluminum alloy
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- aluminium alloy
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- 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
- C23C22/60—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 alkaline aqueous solutions with pH greater than 8
- C23C22/66—Treatment of aluminium or alloys based thereon
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- Chemical Kinetics & Catalysis (AREA)
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- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
The invention provides a method for forming a golden yellow film on the surface of an aluminum alloy and belongs to the technical field of surface treatment of metal materials. The clean aluminum alloy is oxidized in an oxidation coloring solution comprising potassium permanganate, sodium persulfate, sodium acetate and sodium chlorate, and then the aluminum alloy with the golden yellow film on the surface is obtained. According to the method, a process formula is non-toxic and environment-friendly; ingredients of the coloring solution are simple, so that the coloring solution is easy and convenient to prepare; the treatment process is simple; the coloring effect is good; and practical production is facilitated. Besides, the golden yellow film formed on the surface of the aluminum alloy through chemical oxidation has the characteristic that the color becomes dark with rise of oxidation temperature and prolonging of oxidation time.
Description
Technical field
The invention belongs to technical field of metal material surface treatment, particularly relate to a kind of nontoxic aluminum alloy surface chemical oxidation golden color processing method.
Background technology
Aluminium is the metal that consumption is maximum except iron and steel in the world at present.Aluminium alloy is because proportion is little, specific tenacity is high and be widely used in industry-by-industry.But the current potential of aluminium is more negative, in alloy, adding of other metallic elements makes it easily galvanic corrosion occur, and causes serious financial loss.Surface treatment is carried out to aluminium alloy and not only can effectively solve above-mentioned Anticorrosion, the decorative value of aluminium alloy can also be improved simultaneously.
Golden yellow magnificent valuable, be a kind of current color of recent domestic metal, non-metal material surface decoration, but price of gold is expensive, is restricted with golden clothes decorations.The appearance of imitation gold process solves this problem.The traditional electrolysis coloring processes of the many employings of technology for gold imitated by existing aluminium alloy, but this method power consumption large, need specific equipment and clamping apparatus, investment is large, cost is high, and is not suitable for the process of large-scale, subminiature workpiece and complex structure workpiece.Chemical oxidation simulating golden colour technology can improve above-mentioned deficiency.
Traditional aluminum alloy surface process uses chromate conversion, and appearance be golden yellow, seems splendid, be greatly favored by consumers for upholstery, but due to sexavalent chrome be carcinogenic substance, serious pollution is caused to environment.China is execution RoHS Directive in 1 day March in 2007, forbids using the hazardous and noxious substances such as sexavalent chrome in metal finishing production process.In recent years, along with the raising of the development of environmental protection industry and the environmental consciousness of people, many Chrome-free novel procesies are there is, but the surface after these art breading is other colors, the requirement of at present industry and golden yellow Outside decoration good for aluminium alloy corrosion resisting property can not be met, be therefore necessary the golden yellow chromic salt process alternative techniques researching and developing a kind of industry needs.
The people such as Xu Long, Guo Ruiguang, under normal temperature condition, adopt nontoxic potassium permanganate, Na
2s
2o
8, NaF, Sodium dodecylbenzene sulfonate mixed solution, carry out conversion processing, prepare golden yellow zero waste water discharge in aluminum alloy surface.The conversion film adopting this technique to be formed is elementary composition primarily of Al, O, F, Mn, and corrosion resistance nature is good; The people such as easy Aiwa, Li Xuefen are containing Ti(H
2tiF
6)/Zr(H
2zrF
6), NaF, treatment solution in add Weibull, organic inhibitor and manganous sulfate, alloy matrix aluminum obtains the golden yellow conversion film of excellent corrosion-proof performance.The oxidation film coloring of the processing condition gained of these scholar's research is respond well, and excellent corrosion resistance, but the fluorine-containing materials such as the NaF all used in heat-tinting formula, to HUMAN HEALTH, bad environmental, need to improve.
Summary of the invention
The object of the invention is to propose a kind ofly can overcome the innoxious method forming golden yellow rete in aluminum alloy surface of above prior art defect, preparation process.
Technical solution of the present invention is: be placed in by the aluminium alloy of cleaning after the heat-tinting liquid be made up of potassium permanganate, Sodium Persulfate, sodium acetate and sodium chlorate is oxidized, obtain the aluminium alloy that surface has golden yellow rete.
Mostly be containing chromium or the objectionable impurities such as fluorine-containing in the chemical oxidation process formula in the past adopted, the present invention utilizes chemical oxidization method the uniform golden yellow rete of last layer in aluminum alloy surface, technical recipe asepsis environment-protecting of the present invention, coloring liquid composition are simple, it is convenient to prepare, treatment process is simple, and coloring effect is good, is convenient to actual production.In addition, the chemical oxidation described in the present invention has the feature of the increase color burn with oxidizing temperature, oxidization time at the golden yellow coloring film that aluminum alloy surface is formed.
The present invention is relative to prior art, and its advantage is as follows:
1, the chemical oxidation method in the present invention is adopted to carry out surface colour to aluminium alloy, simple to operate compared to additive methods such as electrolysis, power consumption is little, without the need to specific equipment and clamping apparatus, invest little, cost is low, and is applicable to the process of large-scale, subminiature workpiece and complex structure workpiece.
2, compare the heat-tinting formula containing chromium, the objectionable impurities such as fluorine-containing proposed, adopt the present invention to carry out aluminium alloy painted containing the material to HUMAN HEALTH, bad environmental, asepsis environment-protecting.
3, oxidizing solution of the present invention is only containing four kinds of components, and consumption, oxidization time, temperature are all moderate, and coloring liquid composition is simple, and it is convenient to prepare, and treatment process is simple, and coloring effect is good, is convenient to actual production.
Further, in heat-tinting liquid of the present invention, potassium permanganate, Sodium Persulfate, sodium acetate and sodium chlorate composition is respectively 0.5 ~ 2.5g/L, 2 ~ 6g/ L, 0.5 ~ 2.5g/ L and 2.5 ~ 12.5g/ L.Effectively can remove the fluorochemical in original painted formula under this formula, adopt sodium acetate and sodium chlorate composite oxidant can increase the vividness of Film color.
The pH of heat-tinting liquid of the present invention is 10.0 ~ 12.0.Oxidation filming color can be made the darkest, and golden yellow effect is stronger.
During oxidation, the temperature of described heat-tinting liquid is 20 ~ 70 DEG C, and oxidization time is 5 ~ 30min.Along with the rising of temperature, deepened gradually to yellowish brown rete by faint yellow.The change of oxidization time, when 5min, Film color has just become golden yellow, but along with time lengthening, thickness increases.The present invention selects above temperature and time to make efficiency and quality reach comparatively ideal result.
During preferred oxidation, the temperature of described heat-tinting liquid is 55 ~ 65 DEG C, and oxidization time is 5 ~ 10min.
In order to reach higher cleanliness factor, be beneficial to the formation of subsequent oxidation film, the present invention is first with washes of absolute alcohol aluminium alloy, remove the greasy dirt of aluminum alloy surface, then with the alkali sodium hydroxide solution process 30 ~ 60s putting into 60 DEG C after deionization washing, remove the thin native oxide layer of aluminum alloy surface, again after deionized water washing, the aqueous nitric acid dipping 5 ~ 20s putting into 1.5 mol/L reaches the object of neutralization, finally with clear water washing, namely obtains clean aluminium alloy after system is dry.
In order to remove film surface dirt settling, improve the visual appearance of product, the present invention also by the aluminium alloy after oxidation with after deionized water ultrasonic cleaning 3 ~ 5 min, through hot-air seasoning.
Accompanying drawing explanation
Fig. 1,2,3 is respectively the Tafel graphic representation that surface that embodiment 1,2,3 method makes is flavous Al-alloy products.
Embodiment
embodiment 1:
1, aluminum alloy surface pre-treatment:
First adopt dehydrated alcohol to clean aluminum alloy surface, remove the greasy dirt on surface; Again with alkali sodium hydroxide solution 30 s putting into 60 DEG C after deionization washing, remove surperficial thin native oxide layer; After deionized water washing, the dilute nitric acid solution putting into 1.5 mol/l floods 10 s neutralizations; Last clear water washing, airing, stand-by.
2, heat-tinting solution is configured:
With potassium permanganate (KMnO
4, analytical pure) and 0.5 g/l, Sodium Persulfate (Na
2s
2o
8, analytical pure) and 3 g/l, sodium acetate (NaAc, analytical pure) 1 g/l and sodium chlorate (NaClO
3, analytical pure) after 5 g/l mixing, adjust the pH of mixed system for 10.00 with the NaOH of 1.0 mol/l, stand-by.
3, heat-tinting:
Heat-tinting solution is put into after water-bath is heated to 55 DEG C, the aluminium alloy after surface preparation is directly put into heat-tinting solution, after 10 min heat-tintings reactions, takes out aluminium alloy.
4, ultrasonic cleaning 3 min is carried out to aluminium alloy, hot-air seasoning with deionized water, obtain surperficial in flavous Al-alloy products.
5, product effect as shown in Figure 1.
embodiment 2:
1, aluminum alloy surface pre-treatment:
First adopt dehydrated alcohol to clean aluminum alloy surface, remove the greasy dirt on surface; Again with alkali sodium hydroxide solution 35 s putting into 60 DEG C after deionization washing, remove surperficial thin native oxide layer; After deionized water washing, the dilute nitric acid solution putting into 1.5 mol/l floods 15 s neutralizations; Last clear water washing, airing, stand-by.
2, heat-tinting solution is configured:
By potassium permanganate (KMnO
4, analytical pure) and 2 g/l, Sodium Persulfate (Na
2s
2o
8, analytical pure) and 3 g/l, sodium acetate (NaAc, analytical pure) 2.5 g/l and sodium chlorate (NaClO
3, analytical pure) after 12.5 g/l mixing, adjust the pH of mixed system for 11.00 with the NaOH of 1.0 mol/l, stand-by.
3, heat-tinting:
Heat-tinting solution is put into after water-bath is heated to 65 DEG C, the aluminium alloy after surface preparation is directly put into heat-tinting solution, after 5 min heat-tintings reactions, takes out aluminium alloy.
4, ultrasonic cleaning 4 min is carried out to aluminium alloy, hot-air seasoning with deionized water, obtain surperficial in flavous Al-alloy products.
5, product effect as shown in Figure 2.
embodiment 3:
1, aluminum alloy surface pre-treatment:
First adopt dehydrated alcohol to clean aluminum alloy surface, remove the greasy dirt on surface; Again with alkali sodium hydroxide solution 30 s putting into 60 DEG C after deionization washing, remove surperficial thin native oxide layer; After deionized water washing, the dilute nitric acid solution putting into 1.5 mol/l floods 15 s neutralizations; Last clear water washing, airing, stand-by.
2, heat-tinting solution is configured:
By potassium permanganate (KMnO
4, analytical pure) and 2.5 g/l, Sodium Persulfate (Na
2s
2o
8, analytical pure) and 3 g/l, sodium acetate (NaAc, analytical pure) 1.5 g/l and sodium chlorate (NaClO
3, analytical pure) after 7.5 g/l mixing, adjust the pH of mixed system for 12.00 with the NaOH of 1.0 mol/l, stand-by.
3, heat-tinting:
Heat-tinting solution is put into after water-bath is heated to 60 DEG C, the aluminium alloy after surface preparation is directly put into heat-tinting solution, after 5 min heat-tintings reactions, takes out aluminium alloy.
4, ultrasonic cleaning 5 min is carried out to aluminium alloy, hot-air seasoning with deionized water, obtain surperficial in flavous Al-alloy products.
5, product effect as shown in Figure 3.
Claims (7)
1. one kind forms the method for golden yellow rete in aluminum alloy surface, after it is characterized in that the aluminium alloy of cleaning being placed in the heat-tinting liquid be made up of potassium permanganate, Sodium Persulfate, sodium acetate and sodium chlorate is oxidized, obtain the aluminium alloy that surface has golden yellow rete.
2. method according to claim 1, is characterized in that in described heat-tinting liquid, potassium permanganate, Sodium Persulfate, sodium acetate and sodium chlorate composition is respectively 0.5 ~ 2.5g/L, 2 ~ 6g/ L, 0.5 ~ 2.5g/ L and 2.5 ~ 12.5g/ L.
3. method according to claim 1 or 2, is characterized in that the pH of described heat-tinting liquid is 10.0 ~ 12.0.
4. method according to claim 1, when it is characterized in that being oxidized, the temperature of described heat-tinting liquid is 20 ~ 70 DEG C, and oxidization time is 5 ~ 30min.
5. method according to claim 4, when it is characterized in that being oxidized, the temperature of described heat-tinting liquid is 55 ~ 65 DEG C, and oxidization time is 5 ~ 10min.
6. method according to claim 1, it is characterized in that first with washes of absolute alcohol aluminium alloy, then with the alkali sodium hydroxide solution process 30 ~ 60s putting into 60 DEG C after deionization washing, again after deionized water washing, put into the aqueous nitric acid dipping 5 ~ 20s of 1.5 mol/L, finally with clear water washing, after system is dry, namely obtain clean aluminium alloy.
7. method according to claim 1, is characterized in that the aluminium alloy after by oxidation is with after deionized water ultrasonic cleaning 3 ~ 5 min, through hot-air seasoning.
Priority Applications (2)
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CN201510342484.2A CN104894552A (en) | 2015-06-19 | 2015-06-19 | Method for forming golden yellow film on surface of aluminum alloy |
PCT/CN2015/098070 WO2016201935A1 (en) | 2015-06-19 | 2015-12-21 | Method for forming golden yellow film layer on surface of aluminum alloy |
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CN201510342484.2A CN104894552A (en) | 2015-06-19 | 2015-06-19 | Method for forming golden yellow film on surface of aluminum alloy |
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Cited By (6)
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WO2016201935A1 (en) * | 2015-06-19 | 2016-12-22 | 海安县申菱电器制造有限公司 | Method for forming golden yellow film layer on surface of aluminum alloy |
CN106480443A (en) * | 2016-12-02 | 2017-03-08 | 兰州理工大学 | A kind of processing method enabling aluminum alloy to the golden yellow passivating film of surface acquisition |
CN106894012A (en) * | 2017-04-11 | 2017-06-27 | 中南大学 | Aluminium and aluminum alloy surface treatment passivating solution and its application of a kind of manganate as main salt |
EP3276044A4 (en) * | 2015-09-16 | 2018-08-08 | Okuno Chemical Industries Co., Ltd. | Chemical conversion solution for aluminum or aluminum alloy, chemical conversion method, and chemical conversion film |
CN113897606A (en) * | 2020-07-06 | 2022-01-07 | 日本表面化学株式会社 | Metal coloring liquid for chemical conversion treatment and metal coloring treatment method |
JP7573232B2 (ja) | 2020-07-06 | 2024-10-25 | 日本表面化学株式会社 | 化成処理用金属着色液及び金属着色処理方法 |
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CN112779531B (en) * | 2020-12-08 | 2024-02-02 | 广东山之风环保科技有限公司 | Treatment process for coloring black oxide film on metal surface |
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Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016201935A1 (en) * | 2015-06-19 | 2016-12-22 | 海安县申菱电器制造有限公司 | Method for forming golden yellow film layer on surface of aluminum alloy |
EP3276044A4 (en) * | 2015-09-16 | 2018-08-08 | Okuno Chemical Industries Co., Ltd. | Chemical conversion solution for aluminum or aluminum alloy, chemical conversion method, and chemical conversion film |
CN106480443A (en) * | 2016-12-02 | 2017-03-08 | 兰州理工大学 | A kind of processing method enabling aluminum alloy to the golden yellow passivating film of surface acquisition |
CN106480443B (en) * | 2016-12-02 | 2018-10-12 | 兰州理工大学 | A kind of processing method for enabling aluminum alloy to surface and obtaining golden yellow passivating film |
CN106894012A (en) * | 2017-04-11 | 2017-06-27 | 中南大学 | Aluminium and aluminum alloy surface treatment passivating solution and its application of a kind of manganate as main salt |
CN106894012B (en) * | 2017-04-11 | 2019-09-24 | 中南大学 | Aluminium and aluminum alloy surface processing passivating solution and its application of a kind of manganate as main salt |
CN113897606A (en) * | 2020-07-06 | 2022-01-07 | 日本表面化学株式会社 | Metal coloring liquid for chemical conversion treatment and metal coloring treatment method |
JP7573232B2 (ja) | 2020-07-06 | 2024-10-25 | 日本表面化学株式会社 | 化成処理用金属着色液及び金属着色処理方法 |
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