CN103266315B - Preparation of aluminum alloy cobalt salt chemical conversion coating treating fluid - Google Patents
Preparation of aluminum alloy cobalt salt chemical conversion coating treating fluid Download PDFInfo
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- CN103266315B CN103266315B CN201310212147.2A CN201310212147A CN103266315B CN 103266315 B CN103266315 B CN 103266315B CN 201310212147 A CN201310212147 A CN 201310212147A CN 103266315 B CN103266315 B CN 103266315B
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Abstract
The invention relates to a preparation method of aluminum alloy cobalt salt chemical conversion coating treating fluid, belonging to the field of aluminum alloy surface treatment. A porous chemical conversion coating formed by treating aluminum alloy through treating fluid has the characteristics of no chromium, environment friendliness, and good corrosion resistance property, and the like, the treating fluid is prepared from cobalt salt, oxidant, ligand and water, wherein per liter of cobalt salt chemical conversion treating fluid contains the following compositions by weight: 20-50g of cobalt salt, 1-50g of an oxidant, and 2-7g of ligand, and the PH value of the treating fluid ranges from 3 to 4; the cobalt salt is selected from one or two of cobalt-nitrate hydrate and cobalt-chloride hydrate; the oxidant is selected from one or more of lithium permanganate, sodium permanganate, ammonia permanganate and calcium permanganate; and the ligand is selected from one or two of sodium nitrite or sodium acetate.
Description
Technical field
The present invention relates to the process of aviation alloyed aluminium decoration and protective coating.Be specially a kind for the treatment of process of aviation alloyed aluminium environment-friendly chromium-free chemical conversion film, the multi-hole type chemical conversion film formed has excellent solidity to corrosion and coating adhesion after closing, and can replace traditional chromic salts chemical conversion treatment technique.
Background technology
Pure aluminum and its alloy exposes can form the natural oxidation film layer of one deck in atmosphere, but thinner thickness is easily damaged, and solidity to corrosion is poor.Need to use coating process, existing two classes transform rete and are used for coating, adopt porous anode method and chemical oxidization method process to obtain respectively for this reason.
Chemical oxidation treatment is at a certain temperature, makes metallic aluminium and oxidizing solution generation chemical reaction, in the technique of the insoluble oxide film of Surface Creation.Larger than natural oxidation film thickness 100 ~ 200 times of chemical oxide film, compared with anode oxide film, has the advantages such as simple to operate, equipment is simple, cost is low, formation speed is fast, tack is good, can make separately protective layer or as application bottom.Shortcoming is that rete quality is soft, wears no resistance, and carrying occasion is easily destroyed.
The chemical method for treating surface of Al and Alalloy is mainly chromate conversion embrane method.The chromic acid conversion film formed has that film formation time is short, rete is thinner, corrosion resistant type is good, on advantages such as the impact of substrate anti-fatigue performance are little; but chromic salt treatment process not only can produce pollution in treating processes; and the hexavalent chromium compound used in chromic salt chemical conversion is the chemical substance of extremely poison; there is strong toxicity and carcinogenesis; be the highly toxic material of 7 of being ranked first in USEPA (ERA), European Union WEES and RoHS instruction clearly propose strictly to limit it and use.China also 2003 announce, to chromic salt carry out limitation use, find chromic salt for treating this work of thing, oneself is imperative.
The research and development of aluminium alloy non-chromium transformation technology mainly concentrate on following several large system: the conversion of titanium zirconates, molybdate conversion, organic acid chemical conversion, the conversion of high-valency metal salt, the conversion of lithium hydrochlorate, rare-earth salts chemical conversion etc.Wherein the development of cobalt salt conversion processing is more late, belongs to chromiumfree conversion new technology, is characterized in that rete contact resistance is low, solidity to corrosion good, and with coating in conjunction with excellent, be applied to the surface treatment of aerospace, electronics and communication products.
Chinese patent literature CN93101737.8 discloses a kind of preparation method of aluminum alloy surface cobalt salt chemical conversion film.Wherein hydrogen peroxide selected by oxygenant.
This research finds to adopt hydrogen peroxide to have following shortcoming as oxygenant, and have strong impulse smell, consumption is large, and compound method is complicated, is not suitable for extensive use.
For the method for this this research to cobalt salt chemical conversion is improved, select permanganate as oxidation promotor, be mixed with a kind of new cobalt salt chemical conversion treatment solution, it is few that it has consumption, and film layer structure is the advantage such as adjustable flexibly.
Prior art: method disclosed in Chinese patent literature CN93101737.8,
The technology of the present invention: the method for the embodiment of the present invention 1,
With the aluminum alloy materials 10 kilograms of above-mentioned same batch of two kinds of method process, result is as following table:
| Treatment effect | Treatment solution consumption | Treatment time | Solution | Cost | |
| Prior art | Outward appearance is uneven, has aberration | 50L | 20min | Produce a large amount of foam, solution is unstable | 1983.25 yuan/ton |
| The technology of the present invention | Appearance uniform, no color differnece | 30L | 20min | Solution-stabilized | 1887.5 yuan/ton |
Through above contrast experiment, prove that method treatment effect of the present invention is good, more superior than prior art.
Summary of the invention
The object of the invention is to overcome prior art Problems existing, if sexavalent chrome is to the harm of environment and human body, provide a kind of low cost to form the cobalt salt chemical conversion processing method of flexible film layer structure in aluminum alloy surface.
Object of the present invention realizes by following technical scheme.
A kind of aluminum alloy cobalt salt chemical conversion membrane processing method, said method comprising the steps of:
1, aluminum alloy surface pre-treatment;
2, with the process of cobalt salt chemical conversion treatment solution;
3, ultrasonic washing with clean water, dries.
Wherein, step 1, described pre-treatment, method is as follows:
(1) soak oil removing with degreaser, soak time is 10 ~ 30min, to remove the greasy dirt that machining surface adds man-hour;
(2) clear water washing;
(3) put into 60 ~ 80 DEG C of basic solutions to soak 30 ~ 60 seconds, to remove surperficial thin native oxide layer,
(4) clear water washing,
(5) soak 30 ~ 60 seconds with dilute nitric acid solution, neutralization;
(6) clear water washing again.
Wherein said degreaser is selected from: dehydrated alcohol, acetone and other organic solvent.
Described basic solution is: sodium carbonate and sodium hydroxide solution, and often liter of basic solution contains 10 ~ 20g sodium carbonate and 15 ~ 30g sodium hydroxide.
Described dilute nitric acid solution is: the dilute nitric acid solution of 10 ~ 30% volume percent.
Wherein, step 2, described process, method is as follows:
Will through step 1, cobalt salt chemical conversion treatment solution put into by pretreated aluminium alloy, soaks at the temperature of 40 ~ 70 DEG C, and the time is 10 ~ 30min.Wherein said cobalt salt chemical conversion treatment solution is by cobalt salt, oxygenant, part, and water is formulated, and wherein, often liter of cobalt salt chemical conversion treatment solution is containing 20 ~ 50g cobalt salt, and 1 ~ 50g oxygenant, 2 ~ 7g part, the pH value for the treatment of solution is between 3 ~ 4.Wherein said cobalt salt be selected from nitric hydrate cobalt and hydration cobaltous chlorate one or both; Described oxygenant is selected from one or more in high manganese lithium, sodium permanganate, potassium permanganate, ammonium permanganate, calcium permanganate; Described part be selected from Sodium Nitrite or sodium acetate one or both; The compound method of cobalt salt chemical conversion treatment solution is as follows: first dissolve cobalt salt, then dissolved oxidant, finally adds part.Nitric acid or sodium hydroxide is adopted to be reconciled between 3 ~ 4 by the pH value for the treatment of solution.
The present invention is relative to prior art, and its advantage is as follows:
(1) the present invention is applicable to aviation alloyed aluminium surface conversion treatment.Not containing the sexavalent chrome be harmful to environment and human body and trivalent chromium in coating.
(2) adopt permanganate to be oxygenant, when oxygenate content is 1 ~ 10g/L, the film layer structure formed in aluminum alloy surface is multi-hole type, identical with cobalt salt conversion film structure in the past, must carry out closed for second time; When accelerator content is 10 ~ 50g/L, film layer structure is dense form, without the need to closing.
For further illustrating advantage of the present invention, now provide of the present invention and contrast experiment that is prior art:
Accompanying drawing explanation
The scanning electron microscope diagram of Fig. 1 embodiment 1.
The scanning electron microscope diagram of Fig. 2 embodiment 3.
Embodiment
Below in conjunction with example, the present invention will be further described.
Embodiment 1:
1060 aluminum alloy surface cobalt salt chemical conversion process, comprise the steps:
(1) aluminum alloy surface pretreatment process
First 1060 aluminum alloy specimens are put into degreaser oil removing, to remove the greasy dirt that machining surface adds man-hour, soak time is 10min;
Put into 70 DEG C of basic solution 40s after clear water washing and remove surperficial thin native oxide layer, often liter of basic solution is made up of 10g sodium carbonate and 25g sodium hydroxide; After clear water washing, the dilute nitric acid solution putting into 25% volume percent floods 40s neutralization; Last clear water washing.
(2) configuration of cobalt salt chemical conversion treatment solution: often liter of cobalt salt chemical conversion treatment solution is containing 30g hydration cobaltous chlorate, and 2g high manganese lithium, 2g sodium permanganate, 3g part Sodium Nitrite, the pH value for the treatment of solution is 3.
(3) aluminum alloy surface cobalt salt chemical conversion treatment, be the sample that pre-treatment is good is put into 50 DEG C of cobalt salt chemical conversion treatment solutions configured, the time is 20min, running water wash, then ultrasonic washing with clean water 5min after taking out, hot-air seasoning.
Embodiment 2:
2117 aluminum alloy surface cobalt salt chemical conversion process, comprise the steps:
(1) aluminum alloy surface pretreatment process is with embodiment 1
(2) configuration of cobalt salt chemical conversion treatment solution: often liter of cobalt salt chemical conversion treatment solution is containing 30g hydration cobaltous chlorate, and 6g high manganese lithium, 6g sodium permanganate, 3g part Sodium Nitrite, the pH value for the treatment of solution is 3.
(3) aluminum alloy surface cobalt salt chemical conversion treatment, be the sample that pre-treatment is good is put into 50 DEG C of cobalt salt chemical conversion treatment solutions configured, the time is 20min, running water wash, then ultrasonic washing with clean water 5min after taking out, hot-air seasoning.
Embodiment 3:
7050 aluminum alloy surface cobalt salt chemical conversion process, comprise the steps:
(1) aluminum alloy surface pretreatment process
First 7050 aluminum alloy specimens are put into degreaser oil removing, to remove the greasy dirt that machining surface adds man-hour, soak time is 20min;
Put into 60 DEG C of basic solution 30s after clear water washing and remove surperficial thin native oxide layer, often liter of basic solution is made up of 20g sodium carbonate and 15g sodium hydroxide; After clear water washing, the dilute nitric acid solution putting into 35% volume percent floods 30s neutralization; Last clear water washing.
(2) configuration of cobalt salt chemical conversion treatment solution: often liter of cobalt salt chemical conversion treatment solution contains, 20g hydration cobaltous chlorate, 10g nitric hydrate cobalt, 20g high manganese lithium, 10g sodium permanganate, 3g part Sodium Nitrite, the pH value for the treatment of solution is 4.
(3) aluminum alloy surface cobalt salt chemical conversion treatment, be the sample that pre-treatment is good is put into 60 DEG C of cobalt salt chemical conversion treatment solutions configured, the time is 15min, running water wash, then ultrasonic washing with clean water 6min after taking out, hot-air seasoning.
Claims (1)
1. a cobalt salt chemical conversion treatment solution, is characterized in that: it consists of: often liter of cobalt salt chemical conversion treatment solution by 30g hydration cobaltous chlorate, 2g high manganese lithium, 2g sodium permanganate, 3g part Sodium Nitrite and water formulated, the pH value for the treatment of solution is 3.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106297975B (en) * | 2016-08-14 | 2018-01-19 | 何嘉欣 | A kind of high electromagnetic pulse-resisting flexibility aluminium alloy cable and cable making method |
| CN106756969A (en) * | 2017-01-23 | 2017-05-31 | 江苏理工学院 | A kind of cobalt salt black chemical oxidation liquid and its application for aluminium and aluminium alloy |
| CN108103493A (en) * | 2018-01-03 | 2018-06-01 | 江苏理工学院 | A kind of aluminum alloy cobalt salt chemical conversion solution circulation utilization method |
| CN108220947A (en) * | 2018-01-03 | 2018-06-29 | 江苏理工学院 | A kind of cobalt salt chemical conversion solution recycling method |
| CN108165973A (en) * | 2018-01-03 | 2018-06-15 | 江苏理工学院 | A kind of recycling method of cobalt salt chemical conversion solution |
| CN108179408A (en) * | 2018-01-03 | 2018-06-19 | 江苏理工学院 | A kind of cobalt salt chemical conversion solution and its application |
| CN109972131A (en) * | 2019-03-27 | 2019-07-05 | 江苏理工学院 | A kind of preparation method of aluminum alloy surface cobalt salt conversion film |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1090338A (en) * | 1992-06-25 | 1994-08-03 | 波音公司 | The non-chromate oxide membranous layer of aluminum substrate |
| CN101693995A (en) * | 2009-09-08 | 2010-04-14 | 上海波平航空科技有限公司 | Preparation method of aluminum alloy corrosion resistant coating |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1090338A (en) * | 1992-06-25 | 1994-08-03 | 波音公司 | The non-chromate oxide membranous layer of aluminum substrate |
| CN101693995A (en) * | 2009-09-08 | 2010-04-14 | 上海波平航空科技有限公司 | Preparation method of aluminum alloy corrosion resistant coating |
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