CN102234798B - Magnesium alloy surface conversion film forming solution and using method thereof - Google Patents
Magnesium alloy surface conversion film forming solution and using method thereof Download PDFInfo
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- CN102234798B CN102234798B CN 201110214533 CN201110214533A CN102234798B CN 102234798 B CN102234798 B CN 102234798B CN 201110214533 CN201110214533 CN 201110214533 CN 201110214533 A CN201110214533 A CN 201110214533A CN 102234798 B CN102234798 B CN 102234798B
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Abstract
The invention discloses magnesium alloy surface conversion film forming solution and a using method thereof. The magnesium alloy surface conversion film forming solution consists of meta-vanadic acid radical ions and fluosilicic acid radical ions, and the pH value of the magnesium alloy surface conversion film forming solution is regulated to be between 0.5 and 2.5 by using nitric acid or sulfuric acid; the molar concentration of the meta-vanadic acid radical ions is 3.0*10<-4> to 3.0*10<-2> mol/L; and the molar concentration of the fluosilicic acid radical ions is 3.0*10<-4> to 3.0*10<-2> mol/L. After the magnesium alloy subjected to degreasing, acid washing and activating pretreatment is soaked into the magnesium alloy surface conversion film forming solution for 1 to 45 minutes, a conversion film with uniform luster and excellent corrosion resistance can be formed on the surface of the magnesium alloy. The conversion film forming solution and the process flow are simple, low in pollution and high in production efficiency.
Description
Technical field
The invention belongs to field of metal surface treatment technology, relate to Mg alloy surface and handle, particularly a kind of Mg alloy surface transforms film forming liquid and method of use thereof.
Background technology
It is a kind of traditional processing technology that metallic surface chromic salt chemistry transforms (passivation) processing, and a nearly century is widely used in functional coating and decorative coating field with its remarkable anticorrosion and bond properties, like space flight and aviation; Electronics, automobile, pharmacy; Printing; Machinery, chemical industry, food-processing and other production.
The metallic surface chemical conversion handle technology be describe through removing sull that the metallic surface forms naturally pass through on its surface antiseptic property of chemical reaction generation better and with a better new sull of organic coating bonding force or a term of other compound rete.In all conversion film technology; Chromic salt chemistry conversion processing technology is because the conversion film antiseptic property is good, good and technology makes things convenient for economical and effective with the organic coating bond properties; Become the corrosion protection in the last hundred years and handle one of the widest technology of range of application, usually also as the technological criterion of all other conversion films.But because the carinogenicity of chromic salt, the slake of officiallying enroll in the field of metal surface treatment whole world at present bans use of this traditional art breading technology.
Magnesiumalloy is as light metal material commonly used, and it is little to have density, and specific tenacity, specific rigidity are high, and Young's modulus is low, and castability, capability of electromagnetic shielding are good, are easy to advantages such as recovery.Magnesium reserves on earth are very abundant, and as a kind of emerging structured material, it has important use to be worth and application prospects in fields such as automobile, telecommunications and aerospace.But compare with iron and steel, aluminium, magnesium alloy chemical character is active, chemicalstability is low, corrosion-resistant.Therefore, magnesiumalloy must adopt cost-effective chromic salt chemistry conversion method to handle usually, and formed conversion film has superior solidity to corrosion.
At present, in order to replace Mg alloy surface chromic salt chemistry conversion treatment process, people have proposed various chromium-free treatment methods, comprise phosphoric acid salt, permanganate-phosphoric acid salt, stannate, rare earth, organic cpds transformation processing method etc.But all there is some deficiency in these methods.For example, the stannate treatment process exists environmental pollution, shortcoming that corrosion resisting property is general; There is the shortcoming of body eutrophication, corrosion resisting property difference in the phosphatizing method; Permanganate, rare earth processing method exist technological operation unstable, and the organic cpds transformation processing method can't be applied to industrial production owing to there is the shortcoming of corrosion resisting property difference.
One Chinese patent application (application number: 200810126263.1 and 200810201854.0) disclose respectively and a kind of Mg alloy surface is carried out parkerized method; Wherein, application number: 200810126263.1 treatment scheme is following: activation (35 ℃ ~ 55 ℃) → adjustment (55 ℃ ~ 85 ℃) → chemical conversion (35 ℃ ~ 55 ℃).Application number: 200810201854.0 treatment schemees are following: degreasing in advance, degreasing (55 ℃ ~ 65 ℃) → pickling (45 ℃ ~ 55 ℃) → alkali erosion (80 ℃ ~ 90 ℃) → chemical conversion (18 ℃ ~ 60 ℃) → oven dry (120 ℃).Need heat up consumption mass energy and complex treatment process of treating processes in the above-mentioned patent of having announced.Chemical conversion solution comprises phosphoric acid, monocalcium phosphate, water glass, Sodium orthomolybdate, ammonium meta-vanadate etc. in the application number 200810126263.1; Chemical conversion solution comprises phosphoric acid, SODIUM PHOSPHATE, MONOBASIC, nitrocalcite, Supragil GN, ammonium meta-vanadate in the application number 200810201854.0.This shows; Two patent treatment solutions are main salt formation phosphate conversion film with phosphoric acid salt, dihydrogen phosphate all; Reach the purpose of improving corrosion resistance of magnesium alloy through adding other secondary film formers such as metavanadate, but two patents exist all that phosphate radical causes in the waste liquid body eutrophication pollutes and the waste water complicated component, be difficult for problem such as disposal.
USP 7,964,030 discloses a kind of preparation method of magnesiumalloy conversion fluid.This conversion fluid is made up of the aqueous solution of metavanadate and polyhydroxy aromatic compound.Because organic cpds is participated in film formation reaction in this conversion fluid, and organic transformation film erosion resistance is general, SaltSprayTest only reaches present 8 hours industrial application standard, and also there are problems such as aging in organic membrane.In addition, the hyperthermia drying organic membrane that this process using is 100 ℃ has been wasted mass energy.
Summary of the invention
Big for environment pollution in order to solve the existing carcinogenic chromate treating of Mg alloy surface; And other treatment process preservative effect is poor, technological operation is unstable, pollution and the big problem of energy consumption; The objective of the invention is to; Provide a kind of and pollute little, less energy consumption, the stable Mg alloy surface of treatment process changes into membrane technique, forms the superior conversion film of corrosion resisting property at Mg alloy surface.
In order to realize above-mentioned task, the present invention takes following technical solution:
A kind of Mg alloy surface transforms film forming liquid; It is characterized in that; This Mg alloy surface that makes transforms the aqueous solution that film forming liquid is made up of metavanadic acid acid ion and silicofluoric acid acid ion, and the pH value of using nitric acid or sulfuric acid to regulate Mg alloy surface conversion film forming liquid is 0.5 ~ 2.5; Described metavanadic acid radical ion volumetric molar concentration is 3.0 * 10
-4Mol/L ~ 3.0 * 10
-2Mol/L, described silicofluoric acid radical ion volumetric molar concentration is 3.0 * 10
-4Mol/L ~ 3.0 * 10
-2Mol/L.
Described metavanadic acid radical ion is wherein a kind of of metavanadic acid, sodium metavanadate, potassium metavanadate, ammonium meta-vanadate.
Described silicofluoric acid radical ion is wherein a kind of of silicofluoric acid, Sodium Silicofluoride 98min, potassium silicofluoride, magnesium silicofluoride, ammonium silicofluoride.
Above-mentioned Mg alloy surface transforms the method for use of film forming liquid, it is characterized in that, follows these steps to carry out:
1) Mg alloy surface is carried out oil removing, acid-wash activation processing;
2) with the magnesiumalloy after the activation treatment under normal temperature condition, be immersed in Mg alloy surface and transform in the film forming liquid and reacted 1 ~ 45 minute, promptly form conversion film at Mg alloy surface.
The present invention has following advantage:
1) Mg alloy surface of the present invention transforms film forming liquid owing to do not contain chromic salt and phosphoric acid salt, thereby has alleviated the pollution to environment of production process and product greatly.Though contain fluorochemical in the waste water of discharging, with respect to sexavalent chrome and phosphoric acid salt, the degree of fluoride pollution is lighter relatively, it disposes relatively easy.Three kinds of pollutents are as shown in table 1 to the contrast of influence, treatment process and the requirement of environment.、
Three kinds of pollutent contrasts of table 1
2) Mg alloy surface of the present invention transforms film forming liquid and mainly is made up of the aqueous solution of the inorganic system of metavanadic acid radical ion, silicofluoric acid radical ion, irreducibility acid; Overcome aging, the not good shortcoming of erosion resistance that the organic transformation film exists, and system component is simple, technological operation stable, normal temperature is handled and made production cost low.The bonding force of formed conversion film and matrix, organic coating is strong, and 24 hours surperficial no changes of SaltSprayTest have substantially exceeded 8 hours SaltSprayTest standard-required of present industrial application.
Therefore, with former compared with techniques, Mg alloy surface of the present invention transforms film forming liquid not only can obtain that corrosion resisting property is superior, the uniform conversion film of color and luster at Mg alloy surface, and stable processing technique, pollution are little.The energy is handled, saved to normal temperature, simple, the disposal easily of waste water composition, and production efficiency is high, cost is low.
Embodiment
Mg alloy surface of the present invention transforms film forming liquid and method of use thereof, comprises that mainly Mg alloy surface transforms the preparation of film forming liquid, three steps of the surface preparation of magnesiumalloy and conversion film forming:
Step 1, surface preparation:
Adopt Mg alloy surface oil removing degreasing known in those skilled in the art, acid-wash activation to handle;
Step 2, the preparation Mg alloy surface transforms film forming liquid:
Metavanadic acid radical ion volumetric molar concentration is 3.0 * 10
-4Mol/L ~ 3.0 * 10
-2Mol/L;
Silicofluoric acid radical ion volumetric molar concentration is 3.0 * 10
-4Mol/L ~ 3.0 * 10
-2Mol/L;
Regulate pH that Mg alloy surface transforms film forming liquid in 0.5 ~ 2.5 scope with nitric acid or sulfuric acid;
Step 3 transforms film forming:
Magnesiumalloy after the surface preparation under normal temperature condition, is immersed in Mg alloy surface and transforms in the film forming liquid 1 ~ 45 minute, promptly form conversion film at Mg alloy surface.
Below be the specific embodiment that the contriver provides, the invention is not restricted to these embodiment.
Embodiment 1:
To pass through the oil removing degreasing, the pretreated AZ31B type of acid-wash activation magnesiumalloy places ammonium meta-vanadate 2.0 * 10
-3Mol/L, Sodium Silicofluoride 98min 8.0 * 10
-4It is that 1.5 Mg alloy surface transforms in the film forming liquid that mol/L, nitric acid regulate pH, and normal temperature condition reaction down took out washing and drying after 30 minutes, promptly formed one deck conversion film at the AZ31B Mg alloy surface.The conversion film color and luster of present embodiment preparation is even, and neutral salt spray test did not corrode in 20 hours.
Embodiment 2:
To pass through the oil removing degreasing, the pretreated AZ91D type of acid-wash activation magnesiumalloy places ammonium meta-vanadate 1.0 * 10
-2Mol/L, Sodium Silicofluoride 98min 7.0 * 10
-3It is that 1.0 Mg alloy surface transforms in the film forming liquid that mol/L, nitric acid regulate pH, and normal temperature condition reaction down took out washing and drying after 5 minutes, promptly formed one deck conversion film at the AZ91D Mg alloy surface.The conversion film color and luster of present embodiment preparation is even, and neutral salt spray test did not corrode in 24 hours.
Embodiment 3:
To pass through the oil removing degreasing, the pretreated ME20M type of acid-wash activation magnesiumalloy places ammonium meta-vanadate 5.0 * 10
-3Mol/L, Sodium Silicofluoride 98min 1.5 * 10
-3It is that 2.0 Mg alloy surface transforms in the film forming liquid that mol/L, nitric acid regulate pH, and normal temperature condition reaction down took out washing and drying after 10 minutes, promptly formed the even conversion film of one deck color and luster at the ME20M Mg alloy surface, and neutral salt spray test did not corrode in 18 hours.
Claims (3)
1. a Mg alloy surface transforms film forming liquid; It is characterized in that; This Mg alloy surface that makes transforms film forming liquid by metavanadic acid, sodium metavanadate, potassium metavanadate, ammonium meta-vanadate a kind of and silicofluoric acid, Sodium Silicofluoride 98min, potassium silicofluoride, magnesium silicofluoride, ammonium silicofluoride a kind of aqueous solution of forming wherein wherein, and the pH value of using nitric acid or sulfuric acid to regulate this Mg alloy surface conversion film forming liquid is 0.5 ~ 2.5; Described metavanadic acid radical ion volumetric molar concentration is 3.0 * 10
-4Mol/L ~ 3.0 * 10
-2Mol/L, described silicofluoric acid radical ion volumetric molar concentration is 3.0 * 10
-4Mol/L ~ 3.0 * 10
-2Mol/L.
2. the described Mg alloy surface of claim 1 transforms the method for use of film forming liquid, it is characterized in that, follows these steps to carry out:
1) Mg alloy surface is carried out oil removing degreasing, acid-wash activation pre-treatment;
2) with pretreated magnesiumalloy under normal temperature condition, be immersed in Mg alloy surface and transform in the film forming liquid and reacted 1 ~ 45 minute, promptly form conversion film at Mg alloy surface.
3. method of use as claimed in claim 2 is characterized in that, the Mg alloy surface pre-treatment in the described step 1) is that Mg alloy surface oil removing degreasing known in those skilled in the art, acid-wash activation are handled.
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102851659B (en) * | 2012-09-29 | 2014-06-18 | 西安建筑科技大学 | Magnesium alloy surface phosphorus-free chromium-free conversion coating and application method thereof |
| CN105951076A (en) * | 2016-05-25 | 2016-09-21 | 博罗县东明化工有限公司 | Magnesium alloy Zr-Ga-V conversion film treating agent and magnesium alloy Zr-Ga-V conversion film treating method |
| CN107142471A (en) * | 2017-05-08 | 2017-09-08 | 长沙新材料产业研究院有限公司 | Prepare the corrosion-resistant and anti-light oxidation solution and method for penetrating composite membrane of Mg alloy surface |
| CN110670055A (en) * | 2019-11-20 | 2020-01-10 | 安徽汇源镀锌有限公司 | Preparation method of vanadate conversion film on hot galvanizing layer |
| CN112391661A (en) * | 2020-10-29 | 2021-02-23 | 昶宝电子科技(重庆)有限公司 | Formation process of buried magnesium aluminum panel |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101268214A (en) * | 2005-04-14 | 2008-09-17 | 凯密特尔有限责任公司 | Process for forming a well visible non-chromate conversion coating for magnesium and magnesium alloys |
| CN101358343A (en) * | 2008-09-09 | 2009-02-04 | 西南交通大学 | Magnesium alloy alkaline corrosion inhibitor |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6755918B2 (en) * | 2002-06-13 | 2004-06-29 | Ming-Der Ger | Method for treating magnesium alloy by chemical conversion |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101268214A (en) * | 2005-04-14 | 2008-09-17 | 凯密特尔有限责任公司 | Process for forming a well visible non-chromate conversion coating for magnesium and magnesium alloys |
| CN101358343A (en) * | 2008-09-09 | 2009-02-04 | 西南交通大学 | Magnesium alloy alkaline corrosion inhibitor |
Non-Patent Citations (1)
| Title |
|---|
| K. H. Yang et al..Study of vanadium-based chemical conversion coating on the corrosion resistance of magnesium alloy.《Materials Chemistry and Physics》.2007,第101卷480-485. * |
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