CN100535186C - Surface treatment solution for magnesium alloy material and technique for processing magnesium alloy material surface - Google Patents
Surface treatment solution for magnesium alloy material and technique for processing magnesium alloy material surface Download PDFInfo
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- CN100535186C CN100535186C CNB2007100930477A CN200710093047A CN100535186C CN 100535186 C CN100535186 C CN 100535186C CN B2007100930477 A CNB2007100930477 A CN B2007100930477A CN 200710093047 A CN200710093047 A CN 200710093047A CN 100535186 C CN100535186 C CN 100535186C
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Abstract
The present invention relates to a magnesium alloy material surface treating solution and a magnesium alloy material surface treating technology, and is characterized by comprising the following procedures: the metal surface is cleaned according to the usual surface cleaning method of magnesium alloy; the magnesium alloy material is rapidly transferred to a treating solution to be immersed for 0.5 min to 1.0 min and is hot-air dried under the temperature between 50 DEG C and 70 DEG C; a protective film is formed on the surface of the magnesium alloy material. A layer of exquisite, tight and colorful film is formed on the surface of the magnesium alloy with the technique of the invention, thereby achieving a certain decorative effect. The invention can not only have short-term protection on magnesium alloy but also improve the binding force and the corrosion resistance between the organic coating layer and the magnesium alloy substrate.
Description
Technical field
The present invention relates to a kind of process of surface treatment, particularly a kind of process of surface treatment of magnesium alloy materials and be used for the treatment soln of magnesium alloy materials process of surface treatment.
Background technology
Magnesium alloy has higher specific tenacity, specific rigidity and good casting, damping, machining, dimensional stability and good performances such as electromagnetic shielding as the structural metallic materials of density minimum in the present industrial application.Because the decline of the raising of the quality of production, performance and production cost, price, Application of Magnesium and research center of gravity have expanded to civilian (as automobile and electronics etc.) industrial circle from fields such as military project, aircraft industry.The application rate of growth of magnesium alloy in automobile and electronic industry is up to 15%～20%/year in recent years.Application of Magnesium and exploitation are subjected to the great attention of national governments and enterprise in the world day by day, develop into the third-largest metallic substance after iron and steel and aluminium alloy gradually.
Wrought magnesium alloys and diecast magnesium alloy surface structure are easy to generate corrosion, usually need its surface is handled, to increase the barrier propterty of Mg alloy surface.Because the electrochemical bit of MAGNESIUM METAL is about-2.37v; just very easily oxidation in the normal atmospheric environment; this layer oxide film is loose, insecure; can not play the effect of protecting group material; and hindered the surface treatment of magnesium alloy; so it is very difficult that magnesium alloy surface protective is handled, be to hinder one of gordian technique difficult problem that magnesium alloy materials applies.
At present, mainly contain methods such as application processing, chromate conversion coating processing, electroplating processes, electroless plating processing, anodizing, surface heat spraying in the magnesium alloy surface protective treatment process.Using comparatively sophisticated at present is that differential arc oxidation is handled, and this method has shortcomings such as cost is higher, the complex-shaped part difficulty of processing.And the magnesium alloy long-lasting protection method of more generally using is after Mg alloy surface carries out chemical treatment, protects with the organic coating layer again.In addition, in the above-mentioned magnesium alloy surface chemical treatment process, generally all contain heavy metal or rare elements, solution consumption is fast in the protective treatment process, the cost height, and environmental pollution is big.
Summary of the invention
Purpose of the present invention provides a kind of process of surface treatment of magnesium alloy materials.Use technology of the present invention can make Mg alloy surface form the careful colorful film closely of one deck, certain decorative effect is arranged, both can carry out the short-term protection, can improve the bonding force and the solidity to corrosion of organic coating layer and magnesium alloy substrate again magnesium alloy.
The technical scheme of technology of the present invention is: the process of surface treatment of described magnesium alloy materials has following steps:
Method for cleaning surface clean metal surface according to common magnesium alloy; Change over to rapidly in the treatment solution and soaked 0.5-1.0 minute; 50 ℃ of-70 ℃ of warm air dryings form protective film on the magnesium alloy materials surface.
The composition of described film is mainly by MgF
2, MgO forms, the ratio of its amount of substance is about 1: 1, its microscopic particles size is at 150-300nm.
Another object of the present invention, provide a kind of treatment soln that is used for technology of the present invention, treatment soln of the present invention is used for technology of the present invention, the colour film protective capacities that Mg alloy surface is formed is between chromate conversion coating and the phosphate conversion film, Mg alloy surface smooth finish is good, the colorful film of Mg alloy surface has certain decoration function to its outward appearance simultaneously.
Treatment soln of the present invention, one rise that each constituent mass is in the solution:
Citric acid: 3.0-3.5g;
Ammonium bifluoride: 10.0-12.0g;
Thiocarbamide: 1.0-2.5g;
Sodium phosphate 4.0-6.0g;
Zinc nitrate: 2.0-2.5g.
The magnesium alloy materials that is suitable for technology of the present invention is wrought magnesium alloys and diecast magnesium alloy.
Adopt technology of the present invention and treatment soln, Mg alloy surface protected, following advantage is arranged:
1. with the magnesium alloy of art breading of the present invention, its surface forms one deck colour film, and certain decorative effect is arranged.Because the colour film of Mg alloy surface is as thin as a wafer, careful tight, therefore strong with the adhesive ability of matrix, simultaneously.
2. with the magnesium alloy of art breading of the present invention, the colour film that the surface forms has preservative activity, with reference to standard GB 6458-1986, carries out anti-neutral salt spray test to containing golden product through magnesium of the present invention, no white corrosion product occurred in 6 hours, indoor placement no considerable change in 1 year.Therefore, can also place in the indoor long period, play protection and decoration function through the magnesium alloy workpiece that colour film is handled.
With the magnesium alloy of art breading of the present invention, adopt standard GB 9286-1998 that colour film and the common epoxy organic coating sticking power that the surface forms is detected, reach 1 grade; In total thickness is under the epoxy coating and the covering of polyurethane coating layer of 60-80 micron, with reference to standard GB 1771-1991, to carrying out anti-neutral salt spray corrosion test 144 hours through magnesium-alloy material of the present invention, no bubbling produces, and salt-fog resistant time prolongs more than 24 hours than the ordinary magnesium alloy product that scribbles identical coating.
3. common magnesium-alloy material when application if when adopting technologies such as traditional alkali cleaning, pickling as pre-treatment, be difficult to carry out drying,, react with water because magnesium alloy is very active, in drying process, rapid oxidation is formed loose oxide compound, influence follow-up coating's adhesion and protection effect.Adopt technology of the present invention, because the surface at magnesium alloy materials forms thin film, make Mg alloy surface be in passive state, it is dry and not oxidized that magnesium alloy is taken out from the aqueous solution, therefore the technology of the present invention surfacecti proteon that can be used for after the magnesium-alloy material moulding is handled, be a kind of inter process method for anticorrosion treatment, the transition layer of application can be provided again, make follow-up dope layer strong adhesion.
4. owing to adopt technology of the present invention, the film that the magnesium alloy materials surface forms to the erosion of matrix seldom, does not influence the surface size of precision parts as thin as a wafer.
5. compare with the chromate conversion membrane technique, do not have heavy metal toxicity and pollution, compare with the phosphate layer technology, antiseptic power is stronger, and solution consumption is slow, and technology is more stable, and cost is cheaper, reduces environmental pollution greatly.
6. technology of the present invention, the film that the magnesium alloy materials surface forms has certain decorate properties, antiseptic property is inferior to chromate film, organic coating is at the sticking power on the colour film and approaching on phosphate layer, can partly substitute chromate film and phosphate layer, as the pre-treatment transition layer of application, and a middle or short term protection, ornament layer.
Technical recipe of the present invention and technological process are simple, and the treatment time is short, and solution consumption is few, do not need heating, help economizing on resources and the energy.The present invention can be used for the engineering goods field of magnesium alloy materials, as fields such as five metals, electronics, vehicle, military projects.
Description of drawings
Fig. 1 is the electron scanning micrograph of Mg alloy surface colorize film;
Fig. 2 is the surface energy spectral curve of Mg alloy surface colorize film.
Embodiment
Press table 1 configuration treatment soln of the present invention:
Table 1: the composition of treatment soln
Getting the trade mark is the AZ31 extrusion magnesium alloy, the following step is installed the extrusion magnesium alloy product is carried out surface treatment:
1. mechanical scrubbing: with sandblast or sand papering, remove deburring, oxide compound, extruding, wash with additive, processing wet goods foreign matter;
2. alkali cleaning degreasing: use 5g/l sodium hydroxide, 10g/l sodium phosphate, 10g/l yellow soda ash, the washing of 2g/l tensio-active agent mixing solutions, normal temperature agitation treatment 1min; Washing;
3. acid-wash activation: the hydrofluoric acid with 11% embathes, and removes remaining oxide skin and dirt, makes the surface more clean activity; Normal temperature is handled 0.5min, washing;
With the activation after magnesium alloy put into pure water or deionized water Rapid Cleaning after, change the treatment soln immersion treatment 1.0 minutes of the described prescription 1 of table 1 or 2 or 3 respectively rapidly over to, taking-up all can make the extrusion magnesium alloy surface obtain colour film of the present invention through 50 ℃-70 ℃ hot blast drying.
To carry out following performance test respectively through the magnesium alloy workpiece of above-mentioned art breading:
1. scanning electron microscope and surface energy spectrum analysis: as shown in Figure 1 and Figure 2, magnesium alloy is through after the art breading of the present invention, the surface has formed film as thin as a wafer, the microscopic particles of forming film is very tiny, the about 200nm of diameter mainly is elementary composition by Mg, F, O etc., because film is to be formed by connecting by the individual layer compound particles, the peak value that includes the Al element of magnesium alloy substrate in the energy spectrogram occurs, and the peak value of Mg element has strengthened.
2. neutral salt spray test: with reference to the method among the standard GB 6458-1986, to carry out anti-neutral salt spray test through the magnesium-alloy material of art breading of the present invention, condition is 3%NaCl, PH=6.7-7.2,35 ± 1 ℃, spraying was observed once in 2 hours continuously, and sample can occur by 6 hours no white corrosion products.
3. application processing: with the magnesium alloy of short run through art breading of the present invention, spray the epoxy grey paint of 30 micron thickness earlier, the interval is spray black acrylic acid-polyurethane two-component coating after 5 minutes, 50-60 minute drying of 80 ℃-100 ℃ bakings, naturally cooling.The cleaning magnesium-alloy material that equivalent amount is not handled through colorize carries out identical application processing, as the blank contrast experiment who detects.
4. sticking power detects: according to standard GB 9286-1998, above-mentioned coating is respectively got 6 carry out cross-hatching detection test, as the reference standard of coating adhesion.All workpiece coating cross cut tests through art breading of the present invention as a result all reach 1 grade, are not reaching one-level and do not draw the product of lattice experimental grade more than 2/3rds through the workpiece coating of art breading of the present invention.
5. coating neutral salt spray test: with reference to the method among standard GB/T1771-1991, above-mentioned application product is respectively got 6 carry out anti-neutral salt spray test, the anti-neutral salt spray test of magnesium-alloy material through art breading of the present invention, condition is 3%NaCl, PH=6.7-7.2, sprays continuously and observed once in 12 hours by 35 ± 1 ℃, by test of many times, most of sample can produce by 144 hours no bubblings; And the application product that does not pass through art breading of the present invention all at 120 hours with interior generation bubbling phenomenon.
Sample thief is AZ61, AZ such as AZ91 series extrusion magnesium alloy and diecast magnesium alloy, and the materials such as cast magnesium alloys of AM series and ZK series, operate according to embodiment 1 same method, its effect and characteristics and present embodiment are basic identical, so technology of the present invention is applicable to extrusion magnesium alloy and diecast magnesium alloy.
Conclusion:
Magnesium alloy through art breading of the present invention forms bright-coloured colorful film on the surface, and certain decorative effect is arranged, and this film is careful tight, and certain preservative property are arranged, and has certain protection and decoration function.Between application and its pretreatment procedure, utilize art breading of the present invention, effective transition layer can be provided, follow-up dope layer sticking power is protected, and can places the long period, as the inter process anti-corrosion method.Technology of the present invention does not have heavy metal toxicity and pollution, and solution consumption is few, and process stabilizing is with low cost.Can partly substitute chromate film and phosphate layer.
Though the present invention discloses as above with preferred embodiment; right its is not in order to limit the present invention; any person of ordinary skill in the field; without departing from the spirit and scope of the invention; when can doing a little change and improvement, so the present invention's protection domain is as the criterion when looking the claim person of defining.
Claims (3)
1. the process of surface treatment of a magnesium alloy materials is characterized in that, following steps are arranged:
Method for cleaning surface clean metal surface according to common magnesium alloy;
Change over to rapidly and soak 0.5～1.0 minute in the treatment solution, each constituent mass is in described one liter of treatment solution solution: citric acid: 3.0～3.5g; Ammonium bifluoride: 10.0～12.0g; Thiocarbamide: 1.0～2.5g; Sodium phosphate: 4.0～6.0g; Zinc nitrate: 2.0～2.5g; Surplus is a water;
50 ℃～70 ℃ warm air dryings form protective film on the magnesium alloy materials surface.
2. the process of surface treatment of magnesium alloy materials according to claim 1, it is characterized in that: the microscopic particles size of described film is at 150～300nm.
3. the process of surface treatment of magnesium alloy materials according to claim 1, it is characterized in that: the composition of described film is mainly by MgF
2, MgO forms, the ratio of its amount of substance is 1: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100930477A CN100535186C (en) | 2007-11-27 | 2007-11-27 | Surface treatment solution for magnesium alloy material and technique for processing magnesium alloy material surface |
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| CNB2007100930477A CN100535186C (en) | 2007-11-27 | 2007-11-27 | Surface treatment solution for magnesium alloy material and technique for processing magnesium alloy material surface |
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| CN101161862A CN101161862A (en) | 2008-04-16 |
| CN100535186C true CN100535186C (en) | 2009-09-02 |
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| CNB2007100930477A Expired - Fee Related CN100535186C (en) | 2007-11-27 | 2007-11-27 | Surface treatment solution for magnesium alloy material and technique for processing magnesium alloy material surface |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102009039887A1 (en) | 2009-09-03 | 2011-03-17 | Innovent E.V. | Method for surface-treatment of magnesium-containing component, comprises applying a chemical passivating solution that consists of thixotropic agent, on a part of the surface and leaving the passivating solution on the surface |
| BR112012012250B8 (en) * | 2009-11-23 | 2022-10-18 | MetCon LLC | METHODS OF MICROPOLISHING A SURFACE OF A NON-FERROUS METAL WORKPIECE AND OF UNIFORM CONTROLLED SURFACE MATERIAL REMOVAL ON A NON-FERROUS METAL WORKPIECE |
| CN106733546A (en) * | 2016-12-14 | 2017-05-31 | 刘兴旺 | A kind of method of the corrosion-resistant surface treatment of magnadure casting |
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Assignee: Shenzhen Success Technology Co., Ltd. Assignor: Chongqing University of Science & Technology Contract record no.: 2011440020257 Denomination of invention: Surface treatment solution for magnesium alloy material and technique for processing magnesium alloy material surface Granted publication date: 20090902 License type: Exclusive License Open date: 20080416 Record date: 20110621 |
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