CN100577891C - Anodic oxidation method for raising rigidity and corrosion resistance of plated aluminum on surface of metal base - Google Patents
Anodic oxidation method for raising rigidity and corrosion resistance of plated aluminum on surface of metal base Download PDFInfo
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- CN100577891C CN100577891C CN200710012270A CN200710012270A CN100577891C CN 100577891 C CN100577891 C CN 100577891C CN 200710012270 A CN200710012270 A CN 200710012270A CN 200710012270 A CN200710012270 A CN 200710012270A CN 100577891 C CN100577891 C CN 100577891C
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Abstract
This invention relates to an anodic oxidation method for improving hardness and corrosion resistance of aluminum-electroplating coating on metal matrix. The method comprises: electroplating aluminum on the surface of metal material by high-temperature or low-temperature molten salt electroplating method to obtain aluminum-electroplating coating, heating at 200-750 deg.C, treating with alkali, polishing, placing in an electroplating solution, and performing anodic oxidation to obtain an aluminum oxide film with a certain thickness on the surface of the metal material. The obtained aluminum-electroplating coating containing aluminum oxide film has such advantages as high hardness and high corrosion resistance. The method has such advantages as low cost and simple process.
Description
Technical field
The present invention relates to metal surface properties modification technology, relate in particular to a kind of raising plated aluminum on surface of metal base hardness and corrosion proof anode oxidation method.
Background technology
Metallic substance is that modern Application gets the most important engineering materials, particularly ferrous materials occupy extremely important status in production and construction and daily life.But owing to the reason of metallic substance itself and the influence of the surrounding medium when being on active service, the damage of form such as burn into wearing and tearing can take place on its surface unavoidably, and reduced the work-ing life of metallic substance, also cause enormous economic loss to the mankind simultaneously.In the military service process of numerous metallic substance, most damage all occurs in the surface of material.Therefore, the surface property that improves material becomes a kind of efficient ways that improves its work-ing life.
Melt salt Electroplating Aluminum technology as one of material surface modifying technology, by after the surface of metallic substance acquisition one deck Electroplating Aluminum, not only can improve the corrosion resisting property of material significantly, but also have advantages such as the electroplating aluminum coating surface quality height that obtained and production cost be low, thereby caused the great interest of many research workers and relevant manufacturer.Mix at present and melt in the salt or, NaCl and AlCl at KCl at the high temperature of KCl and NaCl
3Low-temperature mixed melt in the salt, adopt electric plating method all can on the surface of some metallic substance, obtain one deck electroplating aluminum coating, and its treatment theory and technology maturation comparatively all.
Though electroplating aluminum coating can be as aluminium (alloy), can spontaneously form thickness on its surface under field conditions (factors) is the amorphous oxide film of 0.01～0.10 μ m, and can improve the corrosion resisting property of metallic substance significantly.But since short texture, the hardness of this layer oxide film low, wear no resistance and the high not enough shortcoming of solidity to corrosion, and the non-crystalline state oxide film that makes this layer form under field conditions (factors) can't be as reliable protective film.Therefore, for the surface hardness that makes metallic substance and corrosion resisting property access by a larger margin raising, take further surface treatment to be necessary fully to electroplating aluminum coating.
Usually aluminium (alloy) anodic oxidation treatment is carried out on aluminium (alloy) parts, and that its treatment technology develops into is also very ripe at present.As long as the processing parameters such as current density, treatment temp and treatment time when selecting suitable electrolytic solution and control to handle just can obtain desired oxide thickness and performance thereof.(CN1144852) reported and use by the anionic compound of complex ability, contain the electrolytic solution that the anionic organic acid of alcohol acid and halogenide forms siliceous aluminium is carried out anodised method as: patent " anode oxidation method of aluminium and the application component that makes of method " thus; Patent " the anodic oxidation thick film preparation of aluminum-copper alloy " (CN1560328) has reported that the electrolytic solution formed with 0.5%～1% phosphoric acid, 0.1%～0.5% oxalic acid or citric acid and 0.05%～0.2% cerous sulfate or lanthanum sulfat carries out anode oxidative treatment method under high temperature and the high density to aluminum-copper alloy; Patent " the wide temperature high speed of aluminium strip anonizing " (CN1100761) has been reported added four kinds of additives in the sulphuric acid soln of 1%～3% oxalic acid and 15%～25%, carry out the method for anodic oxidation treatment in 10～50 ℃ of scopes, its oxidation rate was brought up to 2m/min by former 0.5m/min.Patent " on Al-alloy products fast the method and apparatus of preparation anode oxide film " has been reported the method for carrying out anodic oxidation treatment in 15%～30% sulphuric acid soln in (CN1632178).When anodic oxidation treatment, current density is 3～5A/dm
2, the temperature of electrolytic solution is 20～30 ℃.With this understanding, the film forming speed of oxide film is 1.0～2.2 μ m/min.
And carry out the method for anodic oxidation treatment about the material surface aluminium coated, patent " the normal temperature fast anode oxidation technology of metallized film " (CN 85109238), patent " a kind of method " at iron surface recombination ceramic layer (CN1974845) and patent " preparation method of layer for guarding against pervasion of hydrogen on surface of stainless steel " be to adopt vacuum plating respectively (CN1415783), hot-dip aluminum plating technology and pack aluminizing technology are at non-metal base, iron-based and stainless surface obtain after one deck aluminium coated, adopt anodised method to obtain to have good stability again on its surface, the pellumina of premium propertiess such as density height has improved the hardness of material, performance such as solidity to corrosion and high-temperature oxidation.
The anode oxidative treatment method of the performances such as hardness, solidity to corrosion and high-temperature oxidation on plating (oozing) the aluminium surface of above-mentioned raising aluminium (alloy) and material surface, or all carry out on the surface of very high bulk material in the material monolithic density, or on the surface of the non-metal base of the higher plating of surface compact degree (oozing) aluminium or steel substrate material, carry out.And the electroplating aluminum coating that is obtained on the metal matrix surface is owing to be made up of the crystalline particle of many aluminium, and has many gaps between the particle of aluminium, thereby the compactness of the electroplating aluminum coating that is obtained is lower.This configuration of surface of electroplating aluminum coating will cause electroplating aluminum coating difficulty carry out anodic oxidation treatment, thereby finally make the surface property of electroplating aluminum coating be difficult to be improved.
Summary of the invention
The objective of the invention is at existing problem in the prior art, on treatment process and technology, improve, make the surface of electroplating aluminum coating obtain the pellumina of certain thickness high rigidity and high anti-corrosion, thereby improved the hardness and the solidity to corrosion on metal matrix surface effectively.
Technical solution of the present invention is achieved in that
A kind of raising plated aluminum on surface of metal base hardness and corrosion proof anode oxidation method comprise the steps:
(1) adopts high temperature to melt the method that salt Electroplating Aluminum or low temperature melts the salt Electroplating Aluminum and obtain electroplating aluminum coating at metal material surface, (2) high-temperature heating treatment, (3) alkaline etching and polished finish in advance, (4) place electrolytic solution to carry out anodic oxidation treatment plated aluminum on surface of metal base and obtain certain thickness pellumina;
The Heating temperature scope of described high-temperature heating treatment step is 200～750 ℃.
Described high temperature melts salt Electroplating Aluminum or low temperature, and to melt step that salt Electroplating Aluminum method obtains electroplating aluminum coating at metal material surface be to be that 700 ℃～1100 ℃ KCl and the high temperature of NaCl mix to melt and carries out in the salt or be 100 ℃～240 ℃ KCl, NaCl and AlCl in temperature in temperature
3Low-temperature mixed melt in the salt and carry out.
The heat tracing scope of described high-temperature heating treatment step is 300～700 ℃.
Described metallic substance can be the metallic substance of the arbitrary composition proportion in ferrous materials or copper and the alloy thereof.
Used electrolytic solution is any in sulfuric acid, phosphoric acid, oxalic acid, chromic acid or above-mentioned mixing acid and the electrolytic solution that has added additive in above-mentioned acid in the described anodic oxidation treatment step.
The present invention is by adopting anodic oxidation treatment to melting salt Electroplating Aluminum method at the electroplating aluminum coating that the metal matrix surface obtains, make its surface obtain the pellumina of certain thickness high rigidity and high anti-corrosion, and reach the purpose of performances such as the hardness that can improve plated aluminum on surface of metal base significantly and solidity to corrosion.And because the present invention also has advantages such as cost is low, technology is simple, thereby remarkable economic efficiency and social benefit are arranged.
Embodiment
Embodiment one: the low temperature KCl+NaCl+AlCl when temperature is 150 ℃
3Mix and melt in the salt, it is 7.9A/dm that current density is carried out on Q235 steel surface
2Electroplating processes, make its surface obtain one deck electroplating aluminum coating.The alkaline etching of electroplating aluminum coating in the 6g/L NaOH solution of 500 ℃ high-temperature heating treatment and 3min handle and nitric acid, phosphoric acid and the sulfuric acid mixed solution of 3min in polished finish after, again electroplating aluminum coating is placed the sulphuric acid soln of 200g/L to carry out 40min, current density is 1.5A/dm
2Condition under anodic oxidation treatment.Represent that with electrochemical method the blunt current density of corrosion proof dimension is respectively by the 59HV of original electroplating aluminum coating through the hardness of the electroplating aluminum coating after the anodic oxidation treatment with in 3.5%NaCl solution
0.01With 1.45 (1gI, mA/cm
2) reach the 567HV after the processing
0.01With-0.98 (1gI, mA/cm
2), its hardness value has improved nearly 9 times, has reduced two orders of magnitude and tie up blunt current density.
Embodiment two: at first obtain certain thickness electroplating aluminum coating by melting the salt electric plating method on Q235 steel surface, melting salt system is KCl+NaCl+AlCl
3, temperature is 150 ℃, electric current is that current density is 7.9A/dm
2It is carried out 300 ℃ high-temperature heating treatment, the alkaline etching processing of 3min and the polished finish of 3min.And the mixed solution that used alkaline etching solution and polishing solution are respectively 6g/L NaOH solution and are made up of nitric acid, phosphoric acid and acetic acid.Thereafter, electroplating aluminum coating is placed the sulphuric acid soln of 130g/L to carry out anodic oxidation treatment, oxidization time is 60min again, and current density is 1.5A/dm
2, electroplating aluminum coating is after the processing of said process, and its hardness is by primary 73HV
0.01Bring up to 606HV
0.01
Embodiment three: at first obtain certain thickness electroplating aluminum coating by melting the salt electric plating method on the copper surface, melting salt system is KCl+NaCl+AlCl
3, temperature is 150 ℃, electric current is that current density is 4A/dm
2The electroplating aluminum coating that is obtained is carried out 500 ℃ high-temperature heating treatment successively, carries out the alkaline etching processing of 3min and carry out the polished finish of 3min in the alkaline etching solution of 6g/L NaOH in the mixed polishing solution of being made up of nitric acid, phosphoric acid and sulfuric acid.Afterwards electroplating aluminum coating is placed 8% chromic acid solution to carry out anodic oxidation treatment, oxidization time is 40min, and the corrosion resisting property of its oxide film is significantly improved, and the blunt current density of the dimension in 3.5%NaCl solution is by primary 1.05 (1gI, mA/cm
2) be reduced to-2.13 (1gI, mA/cm
2).
Example four: at first melt the salt electric plating method and obtain certain thickness electroplating aluminum coating on 20 steel surface by high temperature.The used salt system that melts is that salt is melted in the KCl+NaCl mixing, and 800 ℃ of treatment temps, current density are 7.9A/dm
2The electroplating aluminum coating that is obtained is carried out 700 ℃ high-temperature heating treatment successively respectively, carries out the alkaline etching processing of 3min and carry out the polished finish of 3min in the alkaline etching solution of 6g/LNaOH in the mixed polishing solution of being made up of nitric acid, phosphoric acid and sulfuric acid.Afterwards electroplating aluminum coating is placed the sulphuric acid soln of 150g/L to carry out anodic oxidation treatment.Treatment time 60min, current density is 2A/dm
2Electroplating aluminum coating is after above-mentioned anodic oxidation treatment, and its hardness is by primary 68HV
0.01Bring up to 352HV
0.01
Utilize the technology of the present invention that the surface hardness of metal matrix electroplating aluminum coating and corrosion resisting property are greatly enhanced, thereby further enlarged the range of application of metallic substance.
Claims (5)
1, a kind of raising plated aluminum on surface of metal base hardness and corrosion proof anode oxidation method comprise the steps:
(1) adopts high temperature to melt the method that salt Electroplating Aluminum or low temperature melts the salt Electroplating Aluminum and obtain electroplating aluminum coating at metal material surface, (2) high-temperature heating treatment, (3) alkaline etching and polished finish in advance, (4) place electrolytic solution to carry out anodic oxidation treatment plated aluminum on surface of metal base and obtain certain thickness pellumina;
The Heating temperature scope of described high-temperature heating treatment step is 200～750 ℃.
2, raising plated aluminum on surface of metal base hardness according to claim 1 and corrosion proof anode oxidation method, it is characterized in that melting salt Electroplating Aluminum or low temperature by described high temperature, to melt step that salt Electroplating Aluminum method obtains electroplating aluminum coating at metal material surface be to be that 700 ℃～1100 ℃ KCl and the high temperature of NaCl mix to melt and carries out in the salt or be 100 ℃～240 ℃ KCl, NaCl and AlCl in temperature in temperature
3Low-temperature mixed melt in the salt and carry out.
3, raising plated aluminum on surface of metal base hardness according to claim 1 and 2 and corrosion proof anode oxidation method, the heat tracing scope that it is characterized in that described high-temperature heating treatment step is 300～700 ℃.
4, raising plated aluminum on surface of metal base hardness according to claim 3 and corrosion proof anode oxidation method is characterized in that described metallic substance can be the metallic substance of the arbitrary composition proportion in ferrous materials or copper and the alloy thereof.
5, raising plated aluminum on surface of metal base hardness according to claim 4 and corrosion proof anode oxidation method is characterized in that used electrolytic solution in the described anodic oxidation treatment step is any in sulfuric acid, phosphoric acid, oxalic acid, chromic acid or above-mentioned mixing acid and the electrolytic solution that adds some additives in above-mentioned acid.
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| CN200710012270A CN100577891C (en) | 2007-07-25 | 2007-07-25 | Anodic oxidation method for raising rigidity and corrosion resistance of plated aluminum on surface of metal base |
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| CN100577891C true CN100577891C (en) | 2010-01-06 |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101547747B1 (en) * | 2011-03-07 | 2015-08-26 | 애플 인크. | Anodized electroplated aluminum structures and methods for making the same |
| CN103451662B (en) * | 2012-06-01 | 2016-05-04 | 广东欧珀移动通信有限公司 | A kind of stainless surface treatment method |
| CN103540963A (en) * | 2013-10-29 | 2014-01-29 | 常熟市伟达电镀有限责任公司 | Corrosion-resistant electroplating solution |
| CN104152915B (en) * | 2014-05-04 | 2017-09-26 | 昆明理工大学 | A kind of preparation method of aluminic acid zinc protective layer |
| CN105274602A (en) * | 2014-07-09 | 2016-01-27 | 黄燕滨 | Anti-corrosion surface treatment method based on rare-earth modified phosphoric and sulfuric acid anodizing |
| CN104988547B (en) * | 2015-07-07 | 2018-06-15 | 中国科学院过程工程研究所 | A kind of stress relief annealing technique after ionic liquid electroplating bright aluminium |
| CN105951147A (en) * | 2016-05-06 | 2016-09-21 | 江苏国华电力器材有限公司 | Treatment process for abrasion-resistant and corrosion-resistant metal substrate |
| US11261533B2 (en) * | 2017-02-10 | 2022-03-01 | Applied Materials, Inc. | Aluminum plating at low temperature with high efficiency |
| CN110561885A (en) * | 2019-08-30 | 2019-12-13 | 李魁 | Preparation method of high-barrier flexible aluminized film |
| CN110923778A (en) * | 2019-11-28 | 2020-03-27 | 西安昆仑工业（集团）有限责任公司 | Die-casting aluminum surface treatment method |
Citations (1)
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| US4966659A (en) * | 1988-06-03 | 1990-10-30 | Sumitomo Metal Industries, Ltd. | Method for molten salt electroplating of steel |
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|---|---|---|---|---|
| US4966659A (en) * | 1988-06-03 | 1990-10-30 | Sumitomo Metal Industries, Ltd. | Method for molten salt electroplating of steel |
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