CN102181851B - Anhydrous pretreatment method for coating surfaces of magnesium alloys - Google Patents
Anhydrous pretreatment method for coating surfaces of magnesium alloys Download PDFInfo
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- CN102181851B CN102181851B CN2011101005206A CN201110100520A CN102181851B CN 102181851 B CN102181851 B CN 102181851B CN 2011101005206 A CN2011101005206 A CN 2011101005206A CN 201110100520 A CN201110100520 A CN 201110100520A CN 102181851 B CN102181851 B CN 102181851B
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Abstract
The invention provides an anhydrous pretreatment method for coating surfaces of magnesium alloys. The method is characterized by pre-grinding the surfaces of matrix materials; putting the matrix materials into anhydrous ethanol or acetone solution to undergo ultrasonic treatment; drying the matrix materials undergoing ultrasonic treatment with cold air; putting the matrix materials into conversion solution to be converted; washing the converted matrix materials with deionized water and then drying the matrix materials; and putting the matrix materials into phytic acid solution to undergo aftertreatment, washing the matrix materials with the anhydrous ethanol and then drying the matrix materials, wherein the conversion solution comprises the anhydrous ethanol, rare earth salt and a strongly oxidizing accelerator. The method has the following beneficial effects: oxidation and corrosion of magnesium and magnesium of magnesium alloys caused in the pretreatment process are reduced by using the anhydrous solvent, thus improving the adhesion and corrosion resistance of the rare earth salt conversion film layer formed after conversion treatment; and with the organic solution as the solvent, vast organic functional groups can be formed on the surface of the conversion film layer, thus improving the adhesion of the magnesium alloy coating system and realizing effective protection of the magnesium alloys.
Description
Technical field
What the present invention relates to is a kind of pre-treating process of Mg alloy surface application.
Background technology
Magnesiumalloy is 21st century one of metallic substance of application prospect to be arranged most, but its solidity to corrosion is poor, to a great extent limit its application.Therefore, the Mg alloy surface processing is very necessary in practical application.A lot of documents have all been reported the surface treatment method of magnesiumalloy.In numerous anti-corrosion measures, the organic coating resist technology is extremely people's attention owing to have numerous advantages such as technology is simple, with low cost, commercial application prospect is good.
The provide protection of organic coating mainly is between metallic matrix and surrounding medium, to serve as the blocking layer, hinders water, ion, oxygen and electric charge and reaches matrix, stops the formation of open circuit potential.But the factors such as defective that the electrochemical activity of magnesiumalloy self and casting cause have brought very big difficulty for the direct application of the individual layer of traditional coating on magnesiumalloy, mainly show as the following aspects:
(1) the high chemically reactive of magnesiumalloy make one of which run into air or water just form one deck on its surface loose and be the oxide/hydroxide film of alkalescence, this film can reduce the bond quality between follow-up organic coating and matrix; Simultaneously, the chemically reactive that magnesiumalloy is high makes the water, the oxygen equimolecular that are diffused into its interface react with it rapidly, forms bigger concentration gradient, the transmission of accelerating medium in coating with the external world.
(2) the cast magnesium alloys spare surface imperfection that is difficult to avoid and a large amount of holes cause certain difficulty to external coating;
(3) magnesiumalloy creep-resistant property at high temperature is generally very poor, has limited the application of conventional high-temperature Baking Paint on some magnesiumalloy.
Therefore, the protection effect that directly is difficult to obtain in the Mg alloy surface application will obtain the organic coating of high tack, strong solidity to corrosion and aesthetic appearances at Mg alloy surface, and the substrate of correctly selecting the application system is very necessary.
It is the effective ways of magnesium alloy anticorrosion pre-treatment that chemical conversion film is handled, and formed conversion film can improve the solidity to corrosion of matrix, can also improve the tack of application paint film simultaneously.Existing magnesium alloy surface chemical conversion film treatment technology adopts chromatedsolution to handle usually, but employed hexavalent chromium compound is poisonous, and environment is caused serious harm.Rare-earth conversion coatings is the popular research field of magnesium alloy chromium-free environment-friendly type process of surface treatment in recent years, receives numerous investigators' extensive concern because of it is nontoxic, pollution-free and develops rapidly.But because the chemical activity that magnesium matrix is given prominence in the aqueous solution; Make it in the aqueous solution of rare-earth salts, always preferentially form loose oxidation or oxyhydroxide; Cause rare-earth conversion coatings sticking power generally relatively poor, seriously influenced the application and the development of such conversion film.
Summary of the invention
The object of the present invention is to provide a kind of sticking power and corrosion resistance nature that can improve the conversion rete that row forms after the conversion processing; And can improve the sticking power of magnesiumalloy application system, realize anhydrous pre-treating process to the Mg alloy surface application of effective protection of magnesium and magnesiumalloy.
The objective of the invention is to realize like this: a. carries out the pre-grinding processing to magnesiumalloy or magnesium matrix material surface, and then polishes; B. body material is put into absolute ethyl alcohol or acetone soln carries out supersound process 10min; C. will dry up with cold wind through the body material that supersound process is crossed; D. place conversion fluid to carry out conversion processing body material, said conversion fluid is made up of anhydrous ethanol solvent, rare-earth salts and strong oxidizing property promotor; E. after the body material of conversion processing is with deionized water rinsing, dry up; F. body material is put into plant acid solution and carry out aftertreatment 10-20min, dry up after the absolute ethyl alcohol flushing.
The present invention can also comprise:
1, the composition of said conversion fluid comprises rare-earth salts 1-10g/L, strong oxidizing property promotor 20ml/L, and said rare-earth salts is the salt of neodymium, yttrium or gadolinium, and said strong oxidizing property promotor is H
2O
2
2, said conversion processing is carried out under the condition of 20-45 ℃ temperature, pH value 4-7.
3, the treatment time of said conversion processing is 5min-40min.
4, said neodymium salt is Nd (NO
3)
3, yttrium salt is Y (NO
3)
3, gadolinium salt is Gd (NO
3)
3
5, the pH value of conversion fluid adopts and regulates with the corresponding acid of rare-earth salts acid group of the same race.
6, the concentration of said plant acid solution is 5g/L.
Main purpose of the present invention is that the use through anhydrous solvent reduces the oxidation and the corrosion of the magnesium that magnesium and alloy cause in pretreatment procedure; Thereby the rare-earth salts that row forms after the raising conversion processing transforms the sticking power and the corrosion resistance nature of rete; And can form a large amount of organo-functional groups at the conversion film laminar surface as solvent with organic solution; Thereby improve the sticking power of magnesiumalloy application system, realize effective protection magnesium and magnesiumalloy.
For achieving the above object, the principal feature of the technical scheme that adopts of the present invention is: at first, for guaranteeing the carrying out of conversion processing, substrate material surface is carried out leveling and oil removal treatment, for subsequent treatment process provides enough good condition; Then; Putting into the absolute ethyl alcohol is solvent, and in the conversion solution of being made up of rare-earth salts (neodymium, yttrium, gadolinium) and strong oxidizing property promotor, conversion fluid need be placed in the water bath of certain temperature and make solution reach preset temperature; From solution, take out behind the reaction certain hour, with drying up behind the deionized water rinsing; Put into plant acid solution again and carry out aftertreatment, dry up after the absolute ethyl alcohol flushing.
Can find out that from technical scheme the present invention has following beneficial effect:
Anhydrous conversion pre-treatment scheme technology provided by the invention is simple, and ease for operation is strong, and with low cost, and protection effect is obvious, satisfies the demand of economic benefit aspect.
Anhydrous conversion pretreatment technology provided by the present invention can obviously improve the sticking power and the corrosion resistance nature of magnesium alloy rare-earth conversion coatings.
Anhydrous conversion film with a large amount of organo-functional groups provided by the present invention has great importance to sticking power and the erosion resistance that improves magnesiumalloy application system.
The rare-earth salts conversion film that dissolves in absolute ethyl alcohol of the present invention's preparation is that magnesium and Mg alloy surface provide excellent protection; Simultaneously can not produce any harmful effect to environment and human body; Be that the ideal that substitutes traditional chromic acid salt conversion film is selected, have important application prospects.
Description of drawings
The scanning electron microscopy pattern photo that Figure 1A Z91 magnesiumalloy neodymium salt conversion film is handled;
The scanning electron microscopy pattern photo that Fig. 2 AZ91 magnesiumalloy gadolinium salt conversion film is handled;
The scanning electron microscopy pattern photo that Fig. 3 AZ91 magnesiumalloy yttrium salt conversion film is handled.
Embodiment
For example the present invention is done more detailed description below;
Specific embodiments one: the process program that is designed in this embodiment is following: substrate material surface is carried out pre-grinding handle; From 300#-2500#; And then polish with 2.5 oil soluble diamond polishing cream, so that being subsequent treatment process, substrate material surface provide enough good condition to guarantee the carrying out of conversion processing; The sample of handling is put into absolute ethyl alcohol or acetone soln to carry out drying up with cold wind after the supersound process 10min.The sample for preparing is put into conversion fluid, and this rare earth conversion fluid is by 5g/LNd (NO
3)
3With 20ml/L H as promotor
2O
2Form, use absolute ethyl alcohol to be solvent, use HNO
3Regulate the pH value between the 4-5; Then this solution being placed on makes the solution insulation to 30 ℃ in 30 ℃ of water baths; The sample for preparing is put into the conversion solution that configures react 5min, reaction after time of arrival is taken out sample, with drying up after the deionized water complete flushing.Putting into concentration is the anhydrous aftertreatment fluid of phytic acid of 5g/L, at room temperature reacts 15 minutes, cleans to dry up.The neodymium salt conversion film of this scheme gained is fine and close, evenly have preferably sticking power and excellent solidity to corrosion.
Specific embodiments two: this scheme and scheme one difference are that the rare earth conversion fluid is by 5g/L Y (NO
3)
3With 20ml/L H as promotor
2O
2Form, carry out the conversion reaction of 20min through stirring with after regulating the pH value.This programme result shows that it has good solidity to corrosion, can provide good protective action to body material.
Specific embodiments three: this scheme and scheme one difference are that the rare earth conversion fluid is by 10g/L Gd (NO
3)
3With 20ml/L H as promotor
2O
2Form, carry out the conversion reaction of 40min through stirring with after regulating the pH value.This scheme can prepare thicker conversion rete.
Specific embodiments four: this scheme and scheme one difference are that the rare earth conversion fluid is by 5g/L Nd (NO
3)
3With 20ml/L H as promotor
2O
2Form, taking out sample behind the reaction 5min under 45 ℃ the temperature of reaction through stirring with after regulating the pH value.The rete quality that this programme obtains is even, and surface crack is tiny, and solidity to corrosion is good.
Specific embodiments five: this scheme and scheme one difference are that the rare earth conversion fluid is by 10g/L Nd (NO
3)
3With 20ml/L H as promotor
2O
2Form, taking out sample behind the reaction 20min under 45 ℃ the temperature of reaction through stirring with after regulating the pH value.More thick and heavy relatively but surface crack is big relatively than the rete in the scheme four for the rete of this scheme, and solidity to corrosion is better.
Specific embodiments six: this scheme and scheme one difference are that the rare earth conversion fluid is by 1g/L Nd (NO
3)
3With 20ml/L H as promotor
2O
2Form, taking out sample behind the reaction 40min under 45 ℃ the temperature of reaction through stirring with after regulating the pH value.
Specific embodiments seven: this scheme and scheme one difference are that the rare earth conversion fluid is by 10g/L Gd (NO
3)
3With 20ml/L H as promotor
2O
2Form, under 45 ℃, react 5min through stirring with after regulating the pH value and finish.More former kinds of scheme reactions of this reaction are violent, and form thicker rete relatively at short notice, and crackle is distributed in rete uniformly.
Specific embodiments eight: this scheme and scheme one difference are that the rare earth conversion fluid is by 5g/L Gd (NO
3)
3With 20ml/L H as promotor
2O
2Form, react 20min down at 45 ℃ and generated abundant rete through stirring and regulate pH value back, and more similarly be two-layer or trilamellar membrane, but transition to each other be also not obvious, crackle tiny even at random be distributed in each layer.
Specific embodiments nine: this scheme and scheme one difference are that the rare earth conversion fluid is by 1g/L Gd (NO
3)
3With 20ml/L H as promotor
2O
2Form, react 40min down at 45 ℃ through stirring with after regulating the pH value.
Specific embodiments ten: this scheme and scheme one difference are that the pH value is used HNO
3Be adjusted to 6-7, approach neutral solution and show slightly acid and get final product, then scheme one to nine is carried out one time by this potential of hydrogen again.
Specific embodiments 11: this scheme is that used rare earth nitrate in ten kinds of above-mentioned schemes is carried out one time after changing the rare-earth chlorination salt into again, and different is when regulating potential of hydrogen, will use HCl.
The above is merely better instance of the present invention, is not intended to limit the invention, and all any modifications of within the present invention spirit and principle, being done, is equal to and replaces and improvement etc., all belongs in the extent of competence of the present invention.
Claims (9)
1. the pre-treating process of a Mg alloy surface application is characterized in that:
It is following to carry out anhydrous pre-treatment step:
A. magnesiumalloy or magnesium matrix material surface are carried out the pre-grinding processing, and then polish;
B. body material is put into absolute ethyl alcohol or acetone soln carries out supersound process 10min;
C. will dry up with cold wind through the body material that supersound process is crossed;
D. place conversion fluid to carry out conversion processing body material, said conversion fluid is made up of anhydrous ethanol solvent, rare-earth salts and strong oxidizing property promotor;
Behind anhydrous pre-treatment step, carrying out following steps handles:
E. after the body material of conversion processing is with deionized water rinsing, dry up;
F. body material is put into plant acid solution and carry out aftertreatment 10-20min, dry up after the absolute ethyl alcohol flushing.
2. the pre-treating process of Mg alloy surface application according to claim 1; It is characterized in that: the composition of said conversion fluid comprises rare-earth salts 1-10g/L, strong oxidizing property promotor 20ml/L; Said rare-earth salts is the salt of neodymium, yttrium or gadolinium, and said strong oxidizing property promotor is H
2O
2
3. the pre-treating process of Mg alloy surface application according to claim 2 is characterized in that: said conversion processing is carried out under the condition of 20-45 ℃ temperature, pH value 4-7.
4. the pre-treating process of Mg alloy surface application according to claim 3 is characterized in that: the treatment time of said conversion processing is 5min-40min.
5. the pre-treating process of Mg alloy surface application according to claim 4 is characterized in that: the concentration of said plant acid solution is 5g/L.
6. according to the pre-treating process of any one described Mg alloy surface application of claim 1-5, it is characterized in that: said rare-earth salts is the nitrate salt of neodymium, yttrium or gadolinium.
7. according to the pre-treating process of any one described Mg alloy surface application of claim 1-5, it is characterized in that: said rare-earth salts is the hydrochloride of neodymium, yttrium or gadolinium.
8. the pre-treating process of Mg alloy surface application according to claim 6 is characterized in that: the pH value of conversion fluid adopts nitric acid to regulate.
9. the pre-treating process of Mg alloy surface application according to claim 7 is characterized in that: the pH value of conversion fluid adopts nitric acid to regulate.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101005206A CN102181851B (en) | 2011-04-21 | 2011-04-21 | Anhydrous pretreatment method for coating surfaces of magnesium alloys |
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|---|---|---|---|
| CN2011101005206A CN102181851B (en) | 2011-04-21 | 2011-04-21 | Anhydrous pretreatment method for coating surfaces of magnesium alloys |
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| CN102181851B true CN102181851B (en) | 2012-08-22 |
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| CN103805985A (en) * | 2014-02-17 | 2014-05-21 | 南通恒瑞电镀有限公司 | Secondary treatment method for aluminum alloy conversion coating |
| CN105970205A (en) * | 2016-05-18 | 2016-09-28 | 安徽省安庆市金誉金属材料有限公司 | Air conditioner aluminum foil surface passivation solution |
| CN105862022A (en) * | 2016-05-18 | 2016-08-17 | 安徽省安庆市金誉金属材料有限公司 | Aluminum strip surface passivation solution |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3102663B2 (en) * | 1992-10-02 | 2000-10-23 | 三井金属鉱業株式会社 | Pre-painting method and painting method for magnesium alloy products |
| CN1632169A (en) * | 2005-01-17 | 2005-06-29 | 大连理工大学 | Process for magnesium alloy surface treatment |
| CN101671821A (en) * | 2008-09-12 | 2010-03-17 | 中国科学院金属研究所 | Chemical conversion solution and chemical conversion process for magnesium alloy surface treatment |
| CN101818339A (en) * | 2010-03-30 | 2010-09-01 | 海洋王照明科技股份有限公司 | Surface rare-earth film transforming agent and surface rare-earth film transformation processing method of aluminium alloy |
-
2011
- 2011-04-21 CN CN2011101005206A patent/CN102181851B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3102663B2 (en) * | 1992-10-02 | 2000-10-23 | 三井金属鉱業株式会社 | Pre-painting method and painting method for magnesium alloy products |
| CN1632169A (en) * | 2005-01-17 | 2005-06-29 | 大连理工大学 | Process for magnesium alloy surface treatment |
| CN101671821A (en) * | 2008-09-12 | 2010-03-17 | 中国科学院金属研究所 | Chemical conversion solution and chemical conversion process for magnesium alloy surface treatment |
| CN101818339A (en) * | 2010-03-30 | 2010-09-01 | 海洋王照明科技股份有限公司 | Surface rare-earth film transforming agent and surface rare-earth film transformation processing method of aluminium alloy |
Non-Patent Citations (1)
| Title |
|---|
| JP特许第3102663号B2 2000.08.25 |
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