CN1388270A - Multicomponent composite oxide film on surface of magnesium alloy and the oxidizing treatment method - Google Patents
Multicomponent composite oxide film on surface of magnesium alloy and the oxidizing treatment method Download PDFInfo
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- CN1388270A CN1388270A CN 02111520 CN02111520A CN1388270A CN 1388270 A CN1388270 A CN 1388270A CN 02111520 CN02111520 CN 02111520 CN 02111520 A CN02111520 A CN 02111520A CN 1388270 A CN1388270 A CN 1388270A
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Abstract
The present invnetion relates to the surface treatment of magnesium alloy and features that the oxide film formed has the main phase of the composite oxide of Mg, Mn and Mo or Mg, Mo and W or Mg, Mn and V and is dense, close in combining with the base and 5-35 micron thick. The oxidizing treatment solution consists of permanganate or manganate, molybdenate, promoter and stabilizer in certain propertion and the oxidizing treatment process has the conditions of 50-98 deg.c temperature and pH 4-12. The formed composite multielement oxide film has corrosion resistance obviously higher than that formed with chromate and excellent combination with surface paint film.
Description
Technical field:
The present invention relates to polynary complex oxide film of a kind of Mg alloy surface and chemical oxidation treatment method, generate high anti-corrosion protective layer.More precisely be to generate polynary complex oxide film at Mg alloy surface with the chemical oxidation treatment method.Belong to the Mg alloy surface process field.
Background technology:
It is firm that magnesium alloy has a light weight, and performances such as good electromagnetic shielding, heat conduction, damping antidetonation can conveniently reclaim again, have satisfied environmental protection and safe requirement.Market is widely used in fields such as modern communications, household electrical appliances, automobile, aerospace, bike and power tools.Particularly in recent years, obtained fast development in the application of high-grade magnesium goods such as notebook computer casing, digital camera, mobile phone, car component, market outlook are very wide.
But the chemical property of magnesium is active, and the solidity to corrosion of magnesium alloy is very poor, especially in atmosphere that contains salts such as sodium-chlor and environment, very easily corrodes, and has had a strong impact on its use.Along with increasing rapidly of magnesium alloy application demand, press for the surfacecti proteon problem that solves magnesium alloy.
The chemical oxidation of Mg alloy surface is one of important method that strengthens corrosion stability of magnesium alloy.Magnesium alloy through chemical oxidation, forms chemical conversion film (or claiming chemical oxide film) at Mg alloy surface in special chemical oxidation solution.This chemical conversion film has the certain protection effect to magnesium alloy, and the solidity to corrosion of magnesium alloy is improved.The inter process protection against corrosion be applicable to the magnesium goods is usually handled in chemical conversion, perhaps as the good bottom of the further application of magnesium goods.
The common chemical method for oxidation is that chromic salt is the chemical oxidation treatment of main solution, forms chromate protective film the magnesium goods are protected.But the oxidation of chromic salt chemistry does not only meet environmental requirement, and the quality of protective membrane and corrosion resisting property are all undesirable.
The chemical oxidation treatment technology of Chrome-frees such as phosphatizing, molybdate processing, manganate processing is successively developed in the U.S., Japan, Germany, Taiwan etc. in recent years.As: number of patent application CN00133152 is to adopt the permanganate (or manganate) and the phosphatic aqueous solution that Mg alloy surface is carried out chemical oxidation.And for example: constitutional chemistry conversion processing solution such as the oxygen acid compound of the heavy metal of number of patent application CN99104158 employing molybdenum, tungsten, vanadium and sulfuric acid, nitric acid, magnesium alloy to be carried out chemical conversion handle, the surface forms protective membrane.But the solidity to corrosion of these chemical conversion films can only be equivalent to the oxide film of chromate treating, handles though can reach " Chrome-free ", does not still realize on its solidity to corrosion breaking through.
The years of researches result that the inventor carries out for the improvement corrosion stability of magnesium alloy shows, as forming polynary complex oxide film, can significantly improve the corrosion stability of magnesium alloy energy at Mg alloy surface.Therefore, the present invention is directed to the shortcoming and the problem of existing chromic salt, manganate, molybdate treatment technology and patented technology, proposed and to have had the more SIMOXIDE chemical oxidation treatment method imagination of the polynary complex oxide film of premium properties in Mg alloy surface formation.
Summary of the invention:
The objective of the invention is to adopt manganate and molybdate (or tungstate, vanadate) and the mixing solutions of film forming accelerating to carry out chemical oxidation, to guarantee under certain process conditions, forming polynary composite protection film at Mg alloy surface.Performance Detection shows, the chemical treatment method that the inventor provides, formed chemical oxide film when formed its solidity to corrosion of polynary complex oxide film of Mg alloy surface significantly surpasses chromate treating, molybdate processing, the single processing of manganate.Behind the finish coatings, good with the paint film bonding force.Thereby realized " Chrome-free " chemical oxidation treatment of magnesium goods, and made solidity to corrosion that breakthrough raising be arranged.
SIMOXIDE chemical oxidation treatment technological process provided by the invention is as shown in Figure 1:
Through surface finish, activation treatment is washed in skimming treatment to magnesium alloy before surface treatment; After chemical oxidation treatment, also handle through washing and sealing treatment or application.Except that following described two aspects, be the general personnel in present technique field and be familiar with, no longer repeat to set forth.
1, pre-treating technology.
Magnesium alloy must carry out pre-treatment before chemical oxidation treatment, the quality of pre-treatment is directly connected to the bonding force of surface coating, compactness, homogeneity and color.The purpose of pre-treatment is removed surperficial grease exactly, and oxide compound and other adhesions make magnesium alloy component have clean, active surface, for subsequently chemical oxidation is ready to condition.
The pre-treating technology condition is:
A). the degreasing decontamination is handled: adopt commercially available RR-601 efficient cleaner (Shanghai Metal Corrosion ﹠. Protection Techn Co., Ltd's production) at 25-40 ℃, ultrasonic cleaning 3-15min.
B). acid-wash activation is handled: make magnesium alloy surface activation in commercially available RR-602 activator (Shanghai Metal Corrosion ﹠. Protection Techn Co., Ltd's production) solution, condition is a temperature: 25-40 ℃, time 15-200s.
C). washing is all deposited under the normal temperature and is carried out.
2, chemical oxidation treatment solution proportioning and processing condition
Chemical oxidation solution is made up of the water-soluble salt of permanganic acid or manganate, molybdate (or tungstate, vanadate) etc. and film forming accelerating and stablizer (as fluorochemical, silicofluoride, nitrate, phosphoric acid salt, acetate etc.) and deionized water etc.All are their K preferably in the above-mentioned salt, an alkali metal salt and Mg alkaline earth salts such as Na.Specifically consisting of of solution:
Permanganate or manganate 0.1-2M
Molybdate or tungstate or vanadate 0.1-2M
Film forming accelerating and stablizer are as a kind of 0.01-0.5M in fluorochemical, silicofluoride, nitrate, phosphoric acid salt, acetate, the acetate
Deionized water is an amount of
The processing condition of chemical oxidation treatment are:
Temperature: 50～98 ℃
Time: 2～30 minutes
PH value: 4～12
2, the performance of chemical oxide film and composition
The thickness of the formed chemical oxide film of Chrome-free oxide treatment provided by the invention is at the 5-35 micron.
The chemical oxide film that the present invention makes is Mg
2MnO
4, Mg
3Mo
3O
8, Mg
3Mn
3O
8The complex oxide film and the matrix bond of densification that Deng the complex oxide that contains Mg, Mn, Mo (W, V) is the main body phase is tight.The microtexture of oxide film and XRD analysis result such as Fig. 2, shown in Figure 3.
Chemical oxidation treatment of the present invention and chromic salt oxide treatment performance can contrast lists in table 1, as seen form the fine and close complex oxide film of the complex oxide main body phase of Mg, Mn, Mo or Mg, Mo, W or Mg, Mo, V owing to the surface through chemical oxidation treatment of the present invention by table, so solidity to corrosion improves greatly, promptly erosion rate is significantly less than the speed of the oxide film of additive method generation.
Table 1, chemical oxidation treatment of the present invention and chromic salt oxide treatment performance comparison result:
* DOW22 is a base material with the AZ91 magnesium alloy all by a kind of magnesium alloy surface treatment * * of the U.S. DOW chemical company of extensive rice usefulness
| Project * * | SIMOXIDE chemical oxidation (the present invention) | The DOW22* chemical oxidation |
| Erosion rate (g/m 2·h) | ????0.382 | ????0.517 |
| Microhardness (Hv) | ????108 | ????105 |
| Paint film adhesion (cross-hatching) | ????100/100 | ????98/100 |
Description of drawings:
Fig. 1 is the technical process of SIMOXIDE chemical oxidation treatment.
Fig. 2 is a SIMOXIDE oxide film microstructure.
Fig. 3 is that SIMOXIDE oxide film XRD phase composite is analyzed.
Embodiment:
The pre-treating technology of all samples is identical in following 6 enforcements, be: AZ91 magnesium alloy die casting sample is ultrasonic cleaning 8min in 30 ℃ RR-601 efficient cleaner, in 30 ℃ RR-602 solution, activate 30 seconds then, carry out the twice washing, carry out chemical oxidation treatment then, its solution and processing condition are listed in respectively thereafter:
Example 1,
Na
2MoO
4???????????????????????????1.0M
K
2MnO
4????????????????????????????0.4M
Na
2SiF
6???????????????????????????0.1M
NaNo
3??????????????????????????????0.1M
pH???????????????????????????????????9
Oxidizing process: 60 ℃, 10 minutes
Film quality: light yellow even, continuous rete, thickness 9 μ m.
Example 2, solution two:
K
2MnO
4????????????????????????????1.0M
Na
2MoO
4???????????????????????????0.4M
NaF??????????????????????????????????0.1M
Oxidizing process: 70 ℃, 10 minutes
Film quality: golden yellow even, continuous rete, thickness 13 μ m.
Example 3, solution three:
Na
2WO
4????????????????????????????1.0M
K
2MnO
4????????????????????????????0.4M
NaCH
3COO???????????????????????????0.2M
Mg
2SiF
6???????????????????????????0.1M
PH value 12
Oxidizing process: 75 ℃, 15 minutes
Film quality: golden yellow evenly continuous rete, thickness 16 μ m.
Example 4, solution four:
Na
2WO
4??????????????????1.0M
K
2MnO
4??????????????????0.4M
NaF????????????????????????0.1M
Na
2SiO
3?????????????????0.2M
Oxidizing process: 75 ℃, 15 minutes
Film quality: the evenly continuous rete of light golden rod yellow, thickness 15 μ m.
Example 5, solution five:
K
2MnO
4??????????????????1.0M
Na
2VO
4??????????????????0.5M
Na
2SiO
3?????????????????0.2M
PH value 9
Oxidizing process: 70 ℃, 15 minutes
Film quality: golden yellow evenly continuous rete, thickness 13.5 μ m.
Example 6, solution six:
K
2MnO
4??????????????????1.0M
Na
2VO
4??????????????????1.0M
Na
2PO
4???????????????????0.1M
Na
2No
3???????????????????0.1M
Oxidizing process: 60 ℃, 10 minutes
Film quality: golden yellow, evenly continuous rete, thickness 8 μ m.
Claims (4)
1, a kind of multicomponent composite oxide film on surface of magnesium alloy is characterized in that it is is the complex oxide film of the densification of main body phase by the complex oxide that contains Mg, Mn, Mo or Mg, Mn, W or Mg, Mn, V.
2, multicomponent composite oxide film on surface of magnesium alloy according to claim 1 is characterized in that described multicomponent composite oxide film thickness is the 5-35 micron.
3, the chemical treatment method of multicomponent composite oxide film on surface of magnesium alloy according to claim 1 comprises skimming treatment, washing, and activation treatment is characterized in that:
1) the pre-treating technology condition is
A). the degreasing decontamination is handled and is adopted the RR-601 efficient cleaner, at 25-40 ℃, ultrasonic cleaning 3-15min;
B). acid-wash activation is handled and is adopted the RR-602 activator, carries out time 15-200s at 25-40 ℃;
C). washing is all carried out at normal temperatures;
2) chemical oxidation treatment solution proportioning and processing condition
A). consisting of of solution:
Permanganate or manganate 0.1-2M
Molybdate or tungstate or vanadate 0.1-2M
A kind of 0.01-0.5M in film forming accelerating and stablizer or fluorochemical or silicofluoride or nitrate or phosphoric acid salt or acetate or the acetate
Deionized water is an amount of
B). the processing condition of chemical oxidation treatment are:
Temperature: 50～98 ℃
Time: 2～30 minutes
PH value: 4～12
4, the chemical treatment method of multicomponent composite oxide film on surface of magnesium alloy according to claim 3 is characterized in that the salt in the chemical oxidation solution ratio is K, Na an alkali metal salt or Mg alkaline earth salt.
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|---|---|---|---|
| CNB021115206A CN1173074C (en) | 2002-04-27 | 2002-04-27 | Multicomponent composite oxide film on surface of magnesium alloy and the oxidizing treatment method |
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|---|---|---|---|
| CNB021115206A CN1173074C (en) | 2002-04-27 | 2002-04-27 | Multicomponent composite oxide film on surface of magnesium alloy and the oxidizing treatment method |
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|---|---|
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| CN1173074C CN1173074C (en) | 2004-10-27 |
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|---|---|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011080165A1 (en) | 2009-12-31 | 2011-07-07 | Henkel Ag & Co. Kgaa | Surface treatment composition and solution for light metals or alloys thereof and surface treatment method |
| EP2944707A1 (en) * | 2014-05-16 | 2015-11-18 | Fundacion Tecnalia Research & Innovation | Conversion coating process for magnesium alloys |
| CN107250435A (en) * | 2015-09-16 | 2017-10-13 | 奥野制药工业株式会社 | Aluminum or aluminum alloy chemical synthesis treatment liquid, formation processing method and chemical conversion envelope |
| CN114686868A (en) * | 2022-03-31 | 2022-07-01 | 东莞理工学院 | Chromium-free and phosphorus-free conversion solution and preparation method and application thereof |
-
2002
- 2002-04-27 CN CNB021115206A patent/CN1173074C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011080165A1 (en) | 2009-12-31 | 2011-07-07 | Henkel Ag & Co. Kgaa | Surface treatment composition and solution for light metals or alloys thereof and surface treatment method |
| EP2944707A1 (en) * | 2014-05-16 | 2015-11-18 | Fundacion Tecnalia Research & Innovation | Conversion coating process for magnesium alloys |
| CN107250435A (en) * | 2015-09-16 | 2017-10-13 | 奥野制药工业株式会社 | Aluminum or aluminum alloy chemical synthesis treatment liquid, formation processing method and chemical conversion envelope |
| CN114686868A (en) * | 2022-03-31 | 2022-07-01 | 东莞理工学院 | Chromium-free and phosphorus-free conversion solution and preparation method and application thereof |
| CN114686868B (en) * | 2022-03-31 | 2024-05-24 | 东莞理工学院 | Chromium-free and phosphorus-free conversion liquid and preparation method and application thereof |
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| Publication number | Publication date |
|---|---|
| CN1173074C (en) | 2004-10-27 |
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Owner name: SHANGHAI INST. OF MICROSYSTEM AND INFORMATION TEC Free format text: FORMER OWNER: SHANGHAI METAL CORROSION +. PROTECTION TECHN CO., LTD. Effective date: 20061124 |
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Effective date of registration: 20061124 Address after: 200050 No. 865, Changning Road, Shanghai Patentee after: Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences Address before: 200050 No. 865, Changning Road, Shanghai Patentee before: Shanghai Metal Corrosion &. Protection Techn Co., Ltd. |
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Granted publication date: 20041027 Termination date: 20110427 |