CN1089124C - Electrolytic chromophoric method of aluminium and aluminium alloy - Google Patents
Electrolytic chromophoric method of aluminium and aluminium alloy Download PDFInfo
- Publication number
- CN1089124C CN1089124C CN96120286A CN96120286A CN1089124C CN 1089124 C CN1089124 C CN 1089124C CN 96120286 A CN96120286 A CN 96120286A CN 96120286 A CN96120286 A CN 96120286A CN 1089124 C CN1089124 C CN 1089124C
- Authority
- CN
- China
- Prior art keywords
- electrolytic
- aluminium
- chromophoric
- grams per
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Electroplating Methods And Accessories (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
The present invention relates to an electrolytic coloring method of aluminum and aluminum alloy, and in the electrolytic coloring method of aluminum and aluminum alloy, the aluminum or the aluminum alloy is electrolyzed by alternating current and is colored into grey aluminum materials. The electrolytic coloring method of aluminum and aluminum alloy comprises the following steps: the aluminum material or the aluminum alloy material is defatted and is washed by water; the material is etched by alkali and is washed by the water; the material is neutralized and is washed by the water; an anode is electrolyzed and is washed by the water; the grey aluminum materials are obtained by an electrolysis coloring process, a water washing process and a hole sealing process. The electrolytic coloring method of aluminum and aluminum alloy is characterized in that the electrolysis coloring process is carried out by the alternating current at normal temperature, and electrolyzing liquid comprises the metal salts of zinc and tin.
Description
The invention belongs to the electrolysis process method, relate in particular to the electrolytic chromophoric method of a kind of aluminium and aluminium alloy.
The electrolytic chromophoric method of existing use Zinc-tin alloy because the redox potential of zinc and tin has a long way to go, is had any problem on implementation method if directly use the catholyte color development to produce alloy, and addressing this problem needs by reducing Sn
+ 2Redox potential, rising zinc Zn
+ 2Redox potential or strengthen zinc and the ionic concn of tin is recently solved, as English Patent (Brit.pat.1408859), the stannous sulfate that uses in the electrolytic solution is more than 5 grams per liters, so pH value can produce grey between must being controlled at 1 to 1.5, owing to adjust pH value, the conductance (Conductivity) of electrolytic solution is raise, wayward, thus cause producing following problem, 1, the product surface hard film produces softening pitching, 2, shade changes soon, is unfavorable for control.
The object of the present invention is to provide the electrolytic chromophoric method of a kind of aluminium and aluminium alloy, make the processing condition of this method be convenient to control and operation, can reduce the raw materials cost of electrolytic solution, electrolytic chromophoric is effective, to improve the quality of aluminium and aluminum alloy ash color system product.
The present invention adopts following technical scheme:
The electrolytic chromophoric method of aluminium of the present invention and aluminium alloy comprises that degreasing, clear water wash; Alkaline etching, clear water are washed; Neutralization, clear water are washed; Anodizing, clear water are washed; Electrolytic chromophoric, clear water is washed process and sealing of hole process, this method adopts alternating current electrolysis, electrolytic solution is by boric acid, zinc sulfate, stannous sulfate, sulfuric acid, stannous sulfate stablizer and water are formed, the electrolytic chromophoric temperature is a normal temperature, the nitric acid of this method employing 30% carries out degreasing, the sodium hydroxide of employing 10% carries out alkaline etching, the nitric acid of employing 10% neutralizes, anodizing is in the sulphuric acid soln of 180 grams per liter concentration, under the condition of 18 ℃ and 17V volts DS, carry out, treatment time is 25 minutes, the component of electrolytic solution mesoboric acid is 20 to 50 grams per liters, its best component is 30 to 50 grams per liters, the zinc sulfate component is 30 to 90 grams per liters, its best composition is 40 to 70 grams per liters, the component of stannous sulfate is 0.5 to 4.5 grams per liter, its best composition is 1.5 to 4.5 grams per liters, and the vitriolic component is 10 to 50 grams per liters, and its best composition is 15 to 35 grams per liters, the component of stannous sulfate stablizer is 1 to 15 grams per liter, its best composition is 3 to 8 grams per liters, and the voltage of used alternating-current is between 10V to 20V, and the electrolytic chromophoric time is 6 to 15 minutes, the stannous sulfate stablizer can be the aliphatics poly-basic organic acid, can be aromatic organic acid, also can be sulfonic acid, can also be with Sn
+ 4Be reduced to Sn
+ 2Organic acid, the aliphatics poly-basic organic acid can be a tartrate, aromatic organic acid can be a phthalic acid, sulfonic acid can be methylsulphonic acid, the sealing of hole process can be to soak the heat-sealing hole of carrying out in 30 minutes in 85 ℃ hot water, also can be to be to soak the sealing of hole that carried out in 5 to 15 minutes in the aqueous solution of 2 gram liters to handle at nickel content.
The electrolytic chromophoric method of aluminium of the present invention and aluminium alloy uses the alternating current electrolysis color development, adds the metal salt compound of zinc and tin in the electrolytic solution, by the effect of boric acid and zinc sulfate, generates the double salt of zinc, has improved zinc (Zn
+ 2) concentration, simultaneously by strengthening the usage quantity of zinc sulfate, reduce stannous sulfate usage quantity, improve Zn
+ 2/ Sn
+ 2Ion concentration, make Zn
+ 2/ Sn
+ 2Ion concentration be 8: 1, thereby make the electrolysis process condition of this method be convenient to control, and then improved the quality of aluminium and aluminum alloy ash color system product.
Cell liquid of the present invention is subjected to the restriction of boric acid solubleness, so be basic point with boric acid when calculating the usage quantity of each component, obtain the usage quantity of other components again, boric acid solubleness at normal temperatures, greatly about 50 grams per liters, for operational convenience, adopt the boric acid concentration of 30 to 40 grams per liters, calculate zinc sulfate (ZnSO thus
47H
2O) working concentration is 50 to 70 grams per liters, zinc sulfate concentration increases again, gray color development there is not much help, increase cost on the contrary, the concentration of stannous sulfate is controlled at below 5 gram liters, help producing the electrolysis aluminum or aluminum alloy of homogeneous ash color system, add sulfuric acid in the cell liquid, it is the throwing power (Throwing power) when increasing electrolytic chromophoric, so that distribution of current is even in the electrolytic chromophoric, sulfuric acid concentration is controlled between 10 to 50 grams per liters, if be less than 10 grams per liters, can make cathode efficiency low excessively, and cause the staining overlong time and the uneven problem generation that stains if sulfuric acid concentration is higher than 50 grams per liters, then can make product oxide scale film pineization, before the color development after washing phenomenon of fading is arranged, the tranquilizer that adds stannous sulfate in the cell liquid is for fear of tin (Sn
+ 2) instability, the stannous sulfate tranquilizer can be aliphatics poly-basic organic acid, aromatic organic acid and sulfonic acid, its concentration is below 4 grams per liters.
Electrolytic chromophoric method of the present invention adopts normal temperature operation down, voltage control between 10 to 20V, current density 0.4 to 1.4A/dm
2Between, if be lower than 0.4A/dm
2The time, if color development overlong time and influence output is greater than 1.4A/dm
2The time, can cause the product hard film to break.
The processing condition of electrolytic chromophoric of the present invention, because the unit time colour-change is little, when producing, control the homogeneous color of product easily, its from electrolysis to beginning to present the grey needs 6 minutes, by beginning to present grey to presenting the black needs 12 minutes, and the processing method of English Patent GB1408859, because the unit time colour-change is big, when producing, be not easy to control the homogeneous color of product, and color development overlong time, the surface oxidation epithelium of aluminium is easy to produce Song Huaji and comes off, and it to beginning to present the grey needs 27 minutes, only needs 3 minutes by beginning to present grey to presenting black from electrolysis.
Following mask body narration embodiment:
Embodiment one:
With surface-area is 19cm
2Aluminium earlier through 30% nitric acid degreasing, after clear water is washed, use 10% sodium hydroxide alkaline etching again clear water wash, then with in 10% nitric acid and after once more clear water wash standby, anode is placed in the sulphuric acid soln of 180 grams per liters, under the condition of 18 ℃ and volts DS 17V, handled 25 minutes, it is standby to wash the back with clear water, adds boric acid 40 grams in electrolyzer, zinc sulfate 60 grams, sulfuric acid 25 grams, stannous sulfate 2.5 grams and tartrate 1.5 grams add water to 1 liter then, put into anode and corresponding carbon dioxide process carbon electrode, aluminium is carried out electrolytic chromophoric, and the condition of electrolytic chromophoric is to use alternating-current, voltage control is at 18V, and current density is controlled at 0.8A/dm
2, temperature is 25 ℃, the color development time was controlled at 9 minutes, and the aluminium behind electrolytic chromophoric is taken out from electrolyzer, washed the back with clear water and immersed in 85 ℃ the hot water, soaked and carried out the sealing of hole processing in 30 minutes, obtained the grey aluminium product that need.
Embodiment two:
With surface-area is 18cm
2Aluminium alloy earlier through 30% nitric acid degreasing, after clear water is washed, with 10% sodium hydroxide alkaline etching again clear water wash, then with in 10% nitric acid and after once more clear water wash standby, anode is placed in the sulphuric acid soln of 180 gram liters, under the condition of 18 ℃ and volts DS 17V, handled 25 minutes, wash afterwards standby with clear water, in electrolyzer, add boric acid 30 grams, zinc sulfate 50 grams, sulfuric acid 30 grams, stannous sulfate 3 grams, sulfonation salicylic acid 3 grams, add water to 1 liter then, put into anode and corresponding stainless steel electrode, aluminium is carried out electrolytic chromophoric, the electrolytic chromophoric condition is, use alternating-current, voltage control is at 17.4V, and current density is controlled at 0.7A/dm
2, temperature is 25 ℃, the color development time was controlled at 10 minutes, and the aluminium behind electrolytic chromophoric is taken out from electrolyzer, washed the back with clear water and immersed in 85 ℃ the hot water, soaked and carried out the sealing of hole processing in 30 minutes, obtained the grey alloy product that needs.
Embodiment three:
With surface-area is 16cm
2Aluminium earlier through 30% nitric acid degreasing, after clear water is washed, use 10% sodium hydroxide alkaline etching again clear water wash, then with in 10% nitric acid and after once more clear water wash standby, anode is placed in the sulphuric acid soln of 180 grams per liters, under the condition of 18 ℃ and volts DS 17V, handled 25 minutes, wash afterwards standby with clear water, in electrolyzer, add boric acid 30 grams, zinc sulfate 50 grams, sulfuric acid 20 grams, stannous sulfate 1.5 grams, citric acid 3 grams, add water to 1 liter then, put into anode and corresponding carbon dioxide process carbon electrode, aluminium is carried out electrolytic chromophoric, the condition of electrolytic chromophoric is, use alternating-current, voltage control is at 18V, and current density is controlled at 0.8A/dm
2, temperature is 25 ℃, and the color development time was controlled at 9 minutes, and the aluminium behind electrolytic chromophoric is taken out from electrolyzer, and washing back immersion nickel content with clear water is in the aqueous solution of 2 grams per liters, soaks and carries out the sealing of hole processing in 10 minutes, obtains the grey aluminium product that need.
In sum, the electrolytic chromophoric method of aluminium of the present invention and aluminium alloy, processing condition are reasonable in design, and operability is good, control easily in the production, good product quality overcomes the defective of traditional technology method, reaches design purpose.
Claims (11)
1, the electrolytic chromophoric method of a kind of aluminium and aluminium alloy is characterized in that, this method comprises that degreasing, clear water wash; Alkaline etching, clear water are washed; Neutralization, clear water are washed; Anodizing, clear water are washed; Electrolytic chromophoric, clear water are washed process and sealing of hole process, and this method adopts alternating current electrolysis, and electrolytic solution is made up of boric acid, zinc sulfate, stannous sulfate, sulfuric acid, stannous sulfate stablizer, and the electrolytic chromophoric temperature is a normal temperature.
2, the electrolytic chromophoric method of aluminium according to claim 1 and aluminium alloy is characterized in that, described skimming processes is that the nitric acid of employing 30% carries out degreasing.
3, the electrolytic chromophoric method of aluminium according to claim 1 and aluminium alloy is characterized in that, the sodium hydroxide of described alkaline etching process employing 10% carries out alkaline etching.
4, the electrolytic chromophoric method of aluminium according to claim 1 and aluminium alloy is characterized in that, the nitric acid of described N-process employing 10% neutralizes.
5, the electrolytic chromophoric method of aluminium according to claim 1 and aluminium alloy is characterized in that, described anodizing is among the sulphuric acid soln of 180 grams per liter concentration, carries out under the condition of 18 ℃ and 17V volts DS, and the treatment time is 25 minutes.
6, the electrolytic chromophoric method of aluminium according to claim 1 and aluminium alloy, it is characterized in that, the component of described electrolytic solution mesoboric acid is 20 to 50 grams per liters, its best component is 30 to 50 grams per liters, the component of zinc sulfate is 30 to 90 grams per liters, its best composition is 40 to 70 grams per liters, the stannous sulfate component is 0.5 to 4.5 grams per liter, its best composition is 1.5 to 4.5 grams per liters, the vitriolic component is 10 to 50 grams per liters, its best composition is 15 to 35 grams per liters, and the component of stannous sulfate stablizer is 1 to 15 grams per liter, and its best composition is 3 to 8 grams per liters.
7, the electrolytic chromophoric method of aluminium according to claim 1 and aluminium alloy is characterized in that, the current density of described alternating-current is 0.4 to 1.4A/dm
2, its best current density is 0.6 to 1.0A/dm
2, voltage of alternating current is between 10V to 20V.
8, the electrolytic chromophoric method of aluminium according to claim 1 and aluminium alloy is characterized in that, the described electrolytic chromophoric time is 6 to 15 minutes.
9, the electrolytic chromophoric method of aluminium according to claim 1 and aluminium alloy, it is characterized in that, described sealing of hole process can be to soak the heat-sealing hole of carrying out in 30 minutes in 85 ℃ hot water, also can be to be to soak the sealing of hole that carried out in 5 to 15 minutes in the aqueous solution of 2 grams per liters to handle at nickel content.
According to the electrolytic chromophoric method of claim 1,6 described aluminium and aluminium alloy, it is characterized in that 10, described stannous sulfate stablizer can be the aliphatics poly-basic organic acid, can be aromatic organic acid, also can be sulfonic acid, can also be can be with Sn
+ 4Be reduced to Sn
+ 2Organic acid.
11, the electrolytic chromophoric method of aluminium according to claim 9 and aluminium alloy is characterized in that, described aliphatics poly-basic organic acid can be a tartrate, and aromatic organic acid can be a phthalic acid, and sulfonic acid can be methylsulphonic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96120286A CN1089124C (en) | 1996-11-05 | 1996-11-05 | Electrolytic chromophoric method of aluminium and aluminium alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96120286A CN1089124C (en) | 1996-11-05 | 1996-11-05 | Electrolytic chromophoric method of aluminium and aluminium alloy |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1181426A CN1181426A (en) | 1998-05-13 |
| CN1089124C true CN1089124C (en) | 2002-08-14 |
Family
ID=5126250
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96120286A Expired - Fee Related CN1089124C (en) | 1996-11-05 | 1996-11-05 | Electrolytic chromophoric method of aluminium and aluminium alloy |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1089124C (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100562609C (en) * | 2006-05-01 | 2009-11-25 | 燕山大学 | Method at aluminium and aluminum alloy surface one step generation colored oxide film |
| CN102485966A (en) * | 2010-12-06 | 2012-06-06 | 深圳市鹏桑普太阳能股份有限公司 | Process for preparing base material aluminum anode oxide film in absorption coating production |
| CN102534721B (en) * | 2012-02-17 | 2015-03-25 | 上海安美特铝业有限公司 | Method for preparing solar selective absorption film |
| CN103194777B (en) * | 2013-03-27 | 2016-03-30 | 成都阳光铝制品有限公司 | The anode oxidation process of aluminum alloy base material |
| CN103776228A (en) * | 2014-01-27 | 2014-05-07 | 澳柯玛股份有限公司 | Anti-condensation and anti-frosting refrigeration appliance |
| CN104313660B (en) * | 2014-10-31 | 2016-09-14 | 湖州织里天荣铝材添加剂厂 | A kind of novel aluminum alloy pink salt coloring process and coloring liquid |
| CN104651905B (en) * | 2015-01-28 | 2017-11-07 | 永保纳米科技(深圳)有限公司 | Dye auxiliary agent and its operation liquid, and the slow dye handling process of anode aluminium level dyeing are delayed in a kind of anode aluminium level dyeing |
| WO2017214778A1 (en) * | 2016-06-12 | 2017-12-21 | 深圳市恒兆智科技有限公司 | Electrolytic colouring stabiliser, metal profile and colouring method thereof |
| CN111876812B (en) * | 2020-08-01 | 2021-11-05 | 东莞市慧泽凌化工科技有限公司 | Nickel-free electrolytic coloring blackening additive and use method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1408859A (en) * | 1973-07-02 | 1975-10-08 | Piesslinger Ind Baubedarf | Electrolytic process for colouring aluminium and its alloys |
| US4070255A (en) * | 1975-03-06 | 1978-01-24 | Yoshida Kogyo K.K. | Process for electrolytically coloring aluminum and aluminum alloys |
-
1996
- 1996-11-05 CN CN96120286A patent/CN1089124C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1408859A (en) * | 1973-07-02 | 1975-10-08 | Piesslinger Ind Baubedarf | Electrolytic process for colouring aluminium and its alloys |
| US4070255A (en) * | 1975-03-06 | 1978-01-24 | Yoshida Kogyo K.K. | Process for electrolytically coloring aluminum and aluminum alloys |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1181426A (en) | 1998-05-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1089124C (en) | Electrolytic chromophoric method of aluminium and aluminium alloy | |
| CN102877114B (en) | A kind of stainless steel Electropolating hangers stripper and using method | |
| FR2493880A1 (en) | ELECTROLYTES FOR THE DEPOSITION OF TRIVALENT CHROME, EMPLOYING A VANADIUM REDUCER | |
| CN1236109C (en) | Electrochemical method for forming inorganic covering layer on surface of copper material | |
| KR860001286B1 (en) | Method for forming decorative colored streak patterns on the surface of an aluminum shaped article | |
| GB2071151A (en) | Trivalent chromium electroplating | |
| CN106929875B (en) | A method of ferrate is prepared based on carbon plate plating iron | |
| CN1152634A (en) | Aluminium material electrolytic polishing of reversal current method | |
| JPH1171696A (en) | Electrogalvanization of secondary formed article | |
| JPS6240438B2 (en) | ||
| US4236977A (en) | Method for preplating steel surfaces | |
| CA2013123A1 (en) | Electrolytic regeneration of alkaline permanganate etching bath | |
| CA1100087A (en) | Process and apparatus for electrolytic colouration of anodised aluminium | |
| CN110468400A (en) | A kind of aluminum alloy surface environmental protection passivating method | |
| CN1015481B (en) | Sodium salt zn-plating secondary passivation filming technology | |
| CN209383864U (en) | A kind of three electric pole type anode and cathodes separation electrolysis unit | |
| CN113881967B (en) | Impurity removal method for lead electrolyte | |
| CN110117796A (en) | A kind of CuFeO2The preparation method of semiconductor | |
| CN103060886A (en) | Electrolyte for removing tin on surface of copper rod | |
| CN116445964A (en) | Alkaline electrolyzed water oxygen evolution electrode and preparation method and application thereof | |
| CN208151504U (en) | Electrodeposited chromium promotes chromium density devices | |
| TW295605B (en) | Electrolytic process for coloring aluminum and aluminum alloys | |
| CN115961331A (en) | Method for recycling cathode copper from acidic etching waste liquid to replace phosphor copper balls | |
| CN116479440A (en) | Electrode scale inhibition method and device for hydrogen production by seawater electrolysis | |
| SU591531A1 (en) | Method of obtaining alkaline metal hypochloride |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |