CN109957830B - Deplating solution and deplating method for anodic oxide film on surface of aluminum alloy - Google Patents
Deplating solution and deplating method for anodic oxide film on surface of aluminum alloy Download PDFInfo
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- CN109957830B CN109957830B CN201711419822.3A CN201711419822A CN109957830B CN 109957830 B CN109957830 B CN 109957830B CN 201711419822 A CN201711419822 A CN 201711419822A CN 109957830 B CN109957830 B CN 109957830B
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- oxide film
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- anodic oxide
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- 229910000838 Al alloy Inorganic materials 0.000 title claims abstract description 78
- 239000010407 anodic oxide Substances 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 57
- 239000000243 solution Substances 0.000 claims abstract description 42
- 229910052979 sodium sulfide Inorganic materials 0.000 claims abstract description 12
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- 230000000694 effects Effects 0.000 abstract description 16
- 238000005488 sandblasting Methods 0.000 abstract description 13
- 230000003647 oxidation Effects 0.000 abstract description 11
- 238000007254 oxidation reaction Methods 0.000 abstract description 11
- 229910045601 alloy Inorganic materials 0.000 abstract description 3
- 239000000956 alloy Substances 0.000 abstract description 3
- 238000006386 neutralization reaction Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000005498 polishing Methods 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000004043 dyeing Methods 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000005491 wire drawing Methods 0.000 description 3
- 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 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000007743 anodising Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000176 sodium gluconate Substances 0.000 description 2
- 235000012207 sodium gluconate Nutrition 0.000 description 2
- 229940005574 sodium gluconate Drugs 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241001268993 Heterochrosis Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- -1 aluminum ions Chemical class 0.000 description 1
- 238000002048 anodisation reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000005237 degreasing agent Methods 0.000 description 1
- 239000013527 degreasing agent Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F1/00—Electrolytic cleaning, degreasing, pickling or descaling
- C25F1/02—Pickling; Descaling
- C25F1/04—Pickling; Descaling in solution
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
The invention providesThe deplating solution for the anodic oxide film on the surface of the aluminum alloy comprises NaOH and Na2S aqueous solution, wherein the concentration of NaOH in the deplating solution is 6-10g/L, and the Na is2The concentration of S is 10-14 g/L. The invention also provides a deplating method of the anodic oxide film on the surface of the alloy, which comprises the steps of placing the aluminum alloy to be treated in a deplating solution, and electrifying the aluminum alloy to be treated by taking the aluminum alloy to be treated as a cathode, wherein the deplating solution is the deplating solution for the anodic oxide film on the surface of the aluminum alloy. The anodic oxidation deplating can completely remove the oxide film layer and can effectively protect the effects of sand blasting and the like on the surface of the aluminum alloy product.
Description
Technical Field
The invention belongs to the field of electronic products, and mainly relates to an aluminum alloy surface anodic oxide film stripping solution and an aluminum alloy surface anodic oxide film stripping method.
Background
Along with the wider and wider application of the aluminum alloy on the mobile phone shell, the recycling of the aluminum alloy with problems in anodic oxidation is more and more emphasized. At present, the oxide film on the surface of the aluminum alloy is directly removed mainly by directly adopting high-concentration sodium hydroxide, and a part of complex, such as sodium gluconate and the like, is usually added to avoid excessive Al3+And aluminum hydroxide precipitate is generated. However, this method has the following disadvantages: 1) the high-concentration sodium hydroxide has too strong corrosivity, so that the surface of the aluminum alloy has over-corrosion, and the original shapes of sand blasting, wire drawing and the like on the surface of a product cannot be ensured; 2) the reaction is too rapid and uneven, so that the consistency of the surface effect of the product after film stripping is poor, namely the oxide film on the local surface is not removed completely.
Disclosure of Invention
The invention aims to overcome the problems of over-etching or incomplete stripping of an oxide film on the surface of the conventional aluminum alloy, and provides an aluminum alloy surface oxide film stripping solution and an aluminum alloy surface oxide film stripping method which can prevent over-etching and completely remove an oxide film layer.
The invention provides a deplating solution for an anodic oxide film on the surface of an aluminum alloy, which comprises NaOH and Na2S aqueous solution, wherein the concentration of NaOH in the deplating solution is 6-10g/L, and the Na is2The concentration of S is 10-14 g/L.
The invention provides a deplating method of an anodic oxide film on an alloy surface, which comprises the steps of placing an aluminum alloy to be treated in a deplating solution, and electrifying the aluminum alloy to be treated by taking the aluminum alloy to be treated as a cathode, wherein the deplating solution is the deplating solution for the anodic oxide film on the aluminum alloy surface.
The aluminum alloy surface anodic oxide film stripping solution takes low-concentration sodium hydroxide as a corrosion base agent and sodium sulfide as a homogenizing agent. The low-concentration sodium hydroxide mainly plays a role in removing the anodic oxide film, namely the oxide film Al2O3Reacting to form aluminum ions; on the other hand, due to the low concentration, the deplating speed of the anodic oxide film can be well controlled, and the problems that partial areas are over-etched or the partial areas are not completely removed due to the over-quick deplating speed are solved. And the sodium sulfide mainly forms sulfide with cations in the sodium sulfide during deplating, and the formed sulfide can be attached to the part from which the oxide film is removed, so that the part from which the oxide film is removed is protected, over-etching is prevented, and the appearance of the surface of the aluminum alloy is protected.
The method for deplating the anodic oxide film on the surface of the aluminum alloy comprises the steps of placing the aluminum alloy needing to be subjected to oxide film removal in the deplating solution, removing the oxide film by an electrolysis method, wherein the main effect of electrolysis is to further prevent the aluminum from dissolving, so that the original appearance (such as sand blasting and wire drawing) of the surface of an aluminum product can be ensured; and the aluminum alloy after film stripping only needs to be chemically polished to ensure the required luster of the product, and then neutralization, anode and the like can be carried out, so that the step of reforming the appearance on the surface of the aluminum alloy is saved.
Detailed Description
The invention provides a deplating solution for an anodic oxide film on the surface of an aluminum alloy, which comprises NaOH and Na2S aqueous solution, wherein the concentration of NaOH in the deplating solution is 6-10g/L, and the Na is2The concentration of S is 10-14 g/L.
According to the aluminum alloy surface anodic oxide film deplating solution provided by the invention, further, the concentration of NaOH in the deplating solution is 7-9g/L, and the Na is2The concentration of S is 11-13 g/L.
The invention also provides a deplating method of the anodic oxide film on the surface of the alloy, which comprises the steps of placing the aluminum alloy to be treated in a deplating solution, and electrifying the aluminum alloy to be treated by taking the aluminum alloy to be treated as a cathode, wherein the deplating solution is the deplating solution for the anodic oxide film on the surface of the aluminum alloy.
According to the deplating method for the anodic oxide film on the surface of the aluminum alloy, provided by the invention, in order to better remove the anodic oxide film on the surface of the aluminum alloy and prevent the aluminum alloy from being over-etched, preferably, the electrifying voltage is 0.5-10V, and the temperature of the deplating solution is 55-70 ℃.
According to the method for stripping the anodic oxide film on the surface of the aluminum alloy, in order to better strip the oxide film, the method preferably further comprises the step of pretreating the aluminum alloy to be treated before stripping.
In the invention, the pretreatment step comprises oil removal and neutralization steps. The pretreatment such as oil removal and neutralization is a conventional treatment method in the field, and is not described herein again.
The deplating method of the anodic oxide film on the surface of the aluminum alloy can remove the oxide film on the surface of the aluminum alloy and simultaneously keep the original appearance of the surface of the aluminum alloy, such as borax, wire drawing and the like. Therefore, neutralization and re-anodization can be carried out only after the aluminum alloy with the oxide film removed is polished to obtain the required gloss. The method of the invention can not only prevent the aluminum alloy from being over-corroded, but also save the working procedure for the subsequent utilization of the aluminum alloy.
The present invention will be described in detail with reference to specific examples, but the scope of the present invention is not limited thereto.
Example 1
1. Preparing a solution:
dissolving sodium hydroxide and sodium sulfide in water to form deplating solution, wherein the sodium hydroxide is 8g/L, and the sodium sulfide is 12 g/L.
2. Deplating the aluminum alloy anodic oxide film:
(1) hanging the aluminum alloy to be treated on a hanger, and placing the aluminum alloy in a neutral degreasing agent (201130 ml/l of Hill metal cleaner) to degrease for 8min at the temperature of 60 ℃;
(2) performing neutralization reaction on the aluminum alloy to be treated for 20s, wherein the neutralization solution is as follows: 250ml/L nitric acid at normal temperature;
(3) and (3) placing the aluminum alloy to be treated in a deplating tank, wherein the deplating solution is the deplating solution in the step (1), performing electrolytic deplating on an oxide film by taking the aluminum alloy to be treated as a cathode and a carbon plate as an anode, and the temperature and the voltage of the deplating solution are 65 ℃ and 1.5V.
3. Re-anodizing the deplated aluminum alloy
(1) And (3) carrying out neutralization reaction on the deplated aluminum alloy product obtained in the step (2) for 20s, wherein the neutralization solution is as follows: 250ml/L nitric acid at normal temperature;
(2) and (3) chemically polishing the neutralized product, wherein the chemically polishing time is 20s, and chemically polishing liquid is as follows: 700ml/L phosphoric acid and 300ml/L sulphuric acid, and the temperature of the chemical polishing solution is 90 ℃;
(3) and carrying out neutralization reaction on the product for 20s again, wherein the neutralization solution is as follows: 250ml/L nitric acid at normal temperature;
(4) anodic oxidation
Putting the aluminum alloy into an anodic oxidation solution for anodic oxidation, wherein the anodic oxidation solution is 210g/L H2SO4The oxidation time is 70min, the temperature is 10 ℃, and the voltage is 15V;
(5) dyeing hole sealing
After anodic oxidation, the aluminum alloy is subjected to ultrasonic treatment and water washing and then is put into an organic dye tank for dyeing, wherein the organic dye is as follows: oreoye 10510 g/L, Oreoye 1012 g/L; the temperature is 22 ℃, and the dyeing time is 3 min. Then placing the dyed aluminum alloy in hole sealing powder (ODM SEAL-EX hole sealing powder of 8-10 g/L) for hole sealing for 20min, then performing water washing and baking to obtain the treated aluminum alloy A1.
Example 2
An aluminum alloy A2 was produced in the same manner as in example 1, except that the stripping solution was 6g/L sodium hydroxide, 10g/L sodium sulfide, 55 ℃ stripping temperature and 10V stripping voltage.
Example 3
An aluminum alloy A3 was produced in the same manner as in example 1, except that the stripping solution was 10g/L sodium hydroxide, 14g/L sodium sulfide, 70 ℃ stripping temperature and 0.5V stripping voltage.
Comparative example 1
An aluminum alloy CA1 was prepared in the same manner as in example 1, except that the deplating solution was 55g/L sodium hydroxide, 10g/L sodium gluconate and no voltage was applied.
Performance testing
Appearance effect
The appearance of the surface of the aluminum alloy after deplating and after re-anodizing was observed with the naked eye, and the results are shown in table 1.
TABLE 1
| Numbering | Appearance effect of deplated aluminum alloy surface | Appearance effect of aluminum alloy surface after secondary anodic oxidation |
| Practice of Example 1 | Uniform surface metal sand blasting effect and no color difference | Uniform and non-heterochromous, uniform and complete sand blasting effect |
| Practice of Example 2 | Uniform surface metal sand blasting effect and no color difference | Uniform and non-heterochromous, uniform and complete sand blasting effect |
| Practice of Example 3 | Uniform surface metal sand blasting effect and no color difference | Uniform and non-heterochrosis, and uniform and complete sand blasting effectThe sand blasting effect is solid Example 1 and example 2 are less robust |
| Comparison of Example 1 | White overall, unremoved film and corrosion of the surface of the substrate Severe, no sand blasting effect | No new oxide film grows on the whitish part after the film is removed, and the film is heterochromatic and has no color Blasting effect |
As can be seen from Table 1, the anodic oxide film on the surface of the aluminum alloy is deplated by using the aluminum alloy anodic oxidation deplating solution provided by the invention, so that the anodic oxide film can be deplated well, the aluminum alloy base material is not corroded, the surface appearance of the aluminum alloy base material can be maintained, and the deplated aluminum alloy is beneficial to being subjected to anodic oxidation again. In the comparative example, the oxide film on the surface of the aluminum alloy is deplated by the high-concentration sodium hydroxide, the surface of the aluminum alloy is whitish, most of the film layer is not taken out, the surface of the aluminum alloy base material is seriously corroded, the sand blasting effect is avoided, after the anode is performed again, a new oxide film is not grown in the whitish place, and the sand blasting effect is avoided even at the part where the oxide film is generated.
Claims (3)
1. The method for deplating the anodic oxide film on the surface of the aluminum alloy is characterized in that the aluminum alloy to be treated is placed in a deplating solution, the aluminum alloy to be treated is electrified by taking the aluminum alloy to be treated as a cathode, the deplating solution is an aqueous solution containing NaOH and Na2S, the concentration of NaOH in the deplating solution is 6-10g/L, and the concentration of Na2S is 10-14 g/L.
2. The method for deplating the anodic oxide film on the surface of the aluminum alloy according to claim 1, wherein the energization voltage is 0.5 to 10V, and the temperature of the deplating solution is 55 to 70 ℃.
3. The method for deplating the anodic oxide film on the surface of the aluminum alloy according to claim 1, further comprising the step of pretreating the aluminum alloy to be treated before deplating.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711419822.3A CN109957830B (en) | 2017-12-25 | 2017-12-25 | Deplating solution and deplating method for anodic oxide film on surface of aluminum alloy |
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| CN201711419822.3A CN109957830B (en) | 2017-12-25 | 2017-12-25 | Deplating solution and deplating method for anodic oxide film on surface of aluminum alloy |
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| CN109957830B true CN109957830B (en) | 2021-02-23 |
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| CN111020588A (en) * | 2019-11-04 | 2020-04-17 | 博罗县东明化工有限公司 | Stripping treatment method and stripping agent for anode oxide film on surface of seven-series aluminum alloy |
Citations (1)
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| CN105088289A (en) * | 2015-08-12 | 2015-11-25 | 深圳市环翔精饰工业有限公司 | Method for electroplating or deplating aluminum-based copper-inlaid workpiece |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6969457B2 (en) * | 2002-10-21 | 2005-11-29 | General Electric Company | Method for partially stripping a coating from the surface of a substrate, and related articles and compositions |
| CN101845663B (en) * | 2009-03-27 | 2012-03-07 | 比亚迪股份有限公司 | Electrolytic deplating solution and deplating method |
| CN103572306B (en) * | 2012-07-30 | 2016-04-13 | 比亚迪股份有限公司 | For copper surface decoating liquid moving back nickel and preparation method thereof and the method for copper surface nickel of decorporating |
| CN103014735A (en) * | 2012-12-04 | 2013-04-03 | 北京航空航天大学 | Film stripping method for stripping titanium alloy anode oxide film |
| CN105088325B (en) * | 2015-07-20 | 2017-10-20 | 中国船舶重工集团公司第十二研究所 | A kind of strip method of magnetron sputtering amorphous carbon coating |
| CN105648441B (en) * | 2016-01-21 | 2019-05-07 | 瑞声光电科技(常州)有限公司 | Taking off plating solution and its take off electroplating method for aluminium alloy |
| CN107338469B (en) * | 2017-06-01 | 2018-06-19 | 江门市江汇电镀有限公司 | A kind of method of ironware surface zinc layers and chromium passivating layer electrolytic deplating process |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105088289A (en) * | 2015-08-12 | 2015-11-25 | 深圳市环翔精饰工业有限公司 | Method for electroplating or deplating aluminum-based copper-inlaid workpiece |
Non-Patent Citations (1)
| Title |
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| "Investigation of deplating behavior of Pt contact pins in semiconductor Cu electroplating process";Hu, Shao-Yu等;《THIN SOLID FILMS 》;20081201;第1306-1310页 * |
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