CN102808210B - Micro-arc oxidation surface treatment method and product prepared by same - Google Patents

Micro-arc oxidation surface treatment method and product prepared by same Download PDF

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Publication number
CN102808210B
CN102808210B CN201210294614.6A CN201210294614A CN102808210B CN 102808210 B CN102808210 B CN 102808210B CN 201210294614 A CN201210294614 A CN 201210294614A CN 102808210 B CN102808210 B CN 102808210B
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arc oxidation
differential arc
treatment
magnesium alloy
carry
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CN201210294614.6A
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Chinese (zh)
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CN102808210A (en
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郑顺奇
李晓静
倪杨
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宁波市瑞通新材料科技有限公司
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Abstract

The invention provides a micro-arc oxidation treatment method applicable to magnesium and magnesium alloy surfaces and a magnesium alloy product obtained by treatment. The optimal process suitable for MB3 magnesium alloy is obtained by making an intensive study on micro-arc oxidation treatment of the specific MB3 magnesium alloy and conducting a great number of repeated groping studies on the steps and details from pretreatment, micro-arc oxidation treatment to after-treatment, and energy consumption and pollution in treatment are greatly reduced with efficiency and film forming quality guaranteed. Results show that a compact and uniform ceramic oxidation film layer closely combined with a magnesium alloy matrix is generated on the magnesium alloy surface obtained by the micro-arc oxidation treatment process, so that corrosion resistance is greatly improved.

Description

A kind of surface treatment method of differential arc oxidation and goods thereof

Technical field

The present invention relates to the technical field of surface of light alloy, the differential arc oxidation treatment method on light alloy surface and light alloy goods for treated gained, especially a kind of differential arc oxidation treatment method of Mg alloy surface and the magnesium alloy product of treated gained specifically.

Background technology

Differential arc oxidation is a kind of light alloy process for treating surface emerging at home and abroad in recent years, it is placed in specific electrolytic solution by processed matrix metal, electrochemical method is utilized to produce micro-arc discharge phenomenon at matrix surface, under the acting in conjunction of plasma chemistry, thermochemistry and electrochemistry etc., directly base metal surface is become oxide ceramics rete by the nodulizing of microcell instantaneous high-temperature.With other surface treatment methods just like compared with traditional anodic oxidation, differential arc oxidation has the advantage of following uniqueness: both containing high-temperature stable phase in such as oxide membranous layer, again containing a certain amount of amorphous phase, thus rete is made to have excellent combination of strength and toughness and the performance such as wear-resisting, anti-corrosion, anti-oxidant; The electrolytic solution adopted containing Toxic and heavy metal element, is scarcely the treatment process of typical clean environment firendly; Technique is simple, and without the need to gas or vacuum protection during process, the anodic oxidation that treatment temp is more traditional is low; After process, matrix metal size distortion is little.

Due to the plurality of advantages of differential arc oxidation, it worldwide becomes study hotspot very soon, especially for improving all relatively poor light metal of hardness, toughness, wear resistance and solidity to corrosion or its alloy.This wherein, main research object is the differential arc oxidization technique of Aluminum-aluminum alloy, and is also in the starting exploratory stage for the research of other light alloys and metal thereof, does not have system and deep research.

Magnesium alloy has that density is low, energy decay estimation is large, effectiveness is good, specific tenacity and the many merits such as higher than Young's modulus, is the environment-friendly type engineering materials of a kind of ultra-light, excellent property, is described as 21 century desirable electronic products case material.But magnesium is as lively as a cricket metal, Standard Electrode Potentials is lower, chemically reactive is high, can seriously be corroded in general environment, even if at room temperature also can be oxidized in atmosphere, the natural oxide film of generation is loose porous, solidity to corrosion is poor, in addition, the quality of magnesium is softer, wear resistance also comparatively, these problems all significantly limit the widespread use of magnesium alloy.

And adopt the surface of emerging differential arc oxidization technique to magnesium alloy to process, and to obtain ceramic alumina rete, the effective way solved the problem beyond doubt.The present invention is just based on above-mentioned consideration, differential arc oxidization technique for magnesium alloy has carried out careful deep research, all carry out studying in large quantities, systematically to each treatment step and each processing parameter, to obtaining the microarc oxidation treatment process being most suitable for magnesium alloy, meanwhile, the intrinsic problem such as compactness, lack of homogeneity caused due to cell texture overcoming that existing arc differential oxide ceramic layer exists.

Summary of the invention

The object of the present invention is to provide a kind of differential arc oxidation treatment method being applicable to magnesium and alloy surface thereof, thus obtain have suitable thickness, the surface ceramic oxidation film layer of even compact.

For achieving the above object, the present invention adopts following technical scheme to be:

A differential arc oxidation treatment method for magnesium and alloy surface thereof, is characterized in that comprising the steps:

The first, matrix metal is carried out sandblasting, and removing surface and oil contaminant, adopts sand papering subsequently, adopts the grinding turn that 500#-2000# is from coarse to fine, until surperficial no marking;

The second, adopt basic solution to carry out dark skimming treatment, adopt distilled water to clean after dark degreasing for subsequent use;

3rd, in alkaline electrolyte, carry out differential arc oxidation process, wherein adopt the method for boosted voltage gradually, final voltage controls at 300-370V, and current density is at 30mA/cm 2below, the differential arc oxidation treatment time is greater than 20 minutes, and the temperature of electrolytic solution maintains and is less than 40 DEG C;

4th, carry out warm air drying again by after the metal distilled water cleaning after differential arc oxidation process, thus obtain final magnesium alloy product.

Preferably, described differential arc oxidation process for be MB3 magnesium alloy, MB3 quality of magnesium alloy is light, good rigidly, have certain solidity to corrosion and dimensional stability, and the mechanical properties such as shock resistance, wear-resisting, fade performance are all very excellent; Also have high heat conduction and conductivity in addition, nonmagnetic, shielding good and the feature such as nontoxic easy recovery, is one widely applicable in magnesium alloy.But very limited to its differential arc oxidation research carried out at present, the present invention has carried out detailed systematic research based on the feature of MB3 magnesium alloy to its differential arc oxidation just, to develop a kind of microarc oxidation treatment process being applicable to it and using.

Preferably, comprising of the basic solution that described dark skimming treatment adopts: the NaOH of KOH, 130-200g/L of 130-200g/L, the two ratio is 1: 1, methoxyisobutyrate 15-20g/L, dimethyl amine 35-40g/L.Above-mentioned basic solution is adopted to carry out the degreasing effect of dark skimming treatment excellent, the ceramic oxide layer of gained also more dense uniform.

Preferably, consisting of of the alkaline electrolyte of described differential arc oxidation process: the KOH of 200-300g/L, the trisodium citrate of 25-30g/L, the sodium phosphate of 160-180g/L, the Sodium Fluoride of 50-70g/L, the ammonium bifluoride of 20-30g/L, the sodium metaaluminate of 40-70g/L, the cerous nitrate of 1-5g/L and or lanthanum nitrate, surplus is water.Above-mentioned alkaline electrolyte is hardly containing hazardous and noxious substances, and the electric conductivity of its concentration and electrolytic solution is moderate, long service life, film forming speed and quality of forming film good, after adopting above-mentioned alkaline electrolyte to carry out differential arc oxidation process, the ceramic alumina rete dense uniform of Mg alloy surface, aperture is tiny.

Preferably, during described differential arc oxidation process, final voltage controls at 320-340V, and current density is at 15-20mA/cm 2below, the temperature of electrolytic solution maintains 25-30 DEG C, and the treatment time controls at 25-30 minute, in differential arc oxidation treating processes, carries out induction stirring simultaneously, and stirring velocity is 300-400rpm.Adopt above-mentioned processing parameter to carry out differential arc oxidation process, not only effectively reduce the energy consumption in treating processes and pollution, in top, improve film forming efficiency simultaneously, ensure that quality of forming film.

Preferably, after differential arc oxidation process, comprise sealing of hole post-processing step further, described sealing of hole aftertreatment be by differential arc oxidation process after magnesium alloy product be immersed in the sodium silicate solution configured and be put in encloses container, use minipump to vacuumize, to 5mbar, continue 30-40 minute, after goods are taken out, hang in drying oven, be cured.

Advantage of the present invention is: carried out careful deep research to the differential arc oxidation process of specific MB3 magnesium alloy, from pre-treatment, differential arc oxidation process to such an extent as to each step of aftertreatment and details carry out a large amount of repeatedly grope research, obtain the technique of the optimum of applicable MB3 magnesium alloy, under the prerequisite of guaranteed efficiency and quality of forming film, greatly reduce energy consumption and the pollution of process.

Accompanying drawing explanation

Fig. 1 is the Mg alloy surface microstructure morphology in the present invention after surface treatment;

Fig. 2 is the magnesium alloy ceramic coating bed interface microstructure morphology in the present invention after surface treatment;

Fig. 3 is the chemical composition analysis of ceramic alumina rete in the present invention.

Embodiment

Below, the present invention is described in detail for the embodiment of the optimum of being summed up by contriver.

The first, MB3 matrix magnesium alloy is carried out sandblasting, and removing surface and oil contaminant, adopts sand papering subsequently, adopts the grinding turn that 500#-2000# is from coarse to fine, until surperficial no marking;

The second, adopt basic solution to carry out dark skimming treatment, adopt distilled water to clean after dark degreasing for subsequent use; Comprising of the basic solution that described dark skimming treatment adopts: the NaOH of KOH, 15g/L of 150g/L, the two ratio is 1: 1,18g/L methoxyisobutyrate, 35g/L dimethyl amine;

3rd, in alkaline electrolyte, carry out differential arc oxidation process, wherein adopt the method for boosted voltage gradually, final voltage controls at 330V, and current density is at about 16mA/cm 2left and right, in 28 minutes differential arc oxidation treatment times, the temperature of electrolytic solution maintains 27 DEG C; Consisting of of the alkaline electrolyte of described differential arc oxidation process: the trisodium citrate of the KOH of 240g/L, 26g/L, the sodium phosphate of 170g/L, the Sodium Fluoride of 55g/L, the ammonium bifluoride of 25g/L, the sodium metaaluminate of 50g/L, the cerous nitrate of 2g/L and/or lanthanum nitrate, surplus is water; In differential arc oxidation treating processes, carry out induction stirring, stirring velocity is 300rpm simultaneously;

4th, the magnesium alloy product after differential arc oxidation process is immersed in the sodium silicate solution configured and is put in encloses container, use minipump to vacuumize, to 5mbar, continue 35 minutes, after goods are taken out, hang in drying oven, be cured;

5th, carry out warm air drying again by after the metal distilled water cleaning after differential arc oxidation process, thus obtain final magnesium alloy product.

From Fig. 1-3, the magnesium alloy after Microarc Oxidation Surface Treatment of the present invention, the ceramic alumina rete even compact of its Surface Creation, is combined with magnesium alloy substrate closely, and thicknesses of layers reaches as high as about 97 μm, and corrosion resistance nature improves greatly.

Claims (2)

1. a differential arc oxidation treatment method for MB3 Mg alloy surface, is characterized in that comprising the steps:
The first, matrix metal is carried out sandblasting, and removing surface and oil contaminant, adopts sand papering subsequently, adopts the grinding turn that 500#-2000# is from coarse to fine, until surperficial no marking;
Second, basic solution is adopted to carry out dark skimming treatment, distilled water is adopted to clean after dark degreasing for subsequent use, comprising of the basic solution that described dark skimming treatment adopts: the NaOH of KOH, 130-200g/L of 130-200g/L, the two ratio is 1: 1, methoxyisobutyrate 15-20g/L, dimethyl amine 35-40g/L;
3rd, in alkaline electrolyte, carry out differential arc oxidation process, wherein adopt the method for boosted voltage gradually, final voltage controls at 320-340V, and current density is at 15-20mA/cm 2, the differential arc oxidation treatment time controls at 25-30 minute, and the temperature of electrolytic solution maintains 25-30 DEG C, in differential arc oxidation treating processes, carry out induction stirring, stirring velocity is 300-400rpm simultaneously, the KOH of consisting of of described alkaline electrolyte: 200-300g/L, the trisodium citrate of 25-30g/L, the sodium phosphate of 160-180g/L, the Sodium Fluoride of 50-70g/L, the ammonium bifluoride of 20-30g/L, the sodium metaaluminate of 40-70g/L, the cerous nitrate of 1-5g/L and or lanthanum nitrate, surplus is water;
4th, after differential arc oxidation process, carry out sealing of hole post-processing step, described sealing of hole aftertreatment be by differential arc oxidation process after magnesium alloy product be immersed in the sodium silicate solution configured and be put in encloses container, use minipump to vacuumize, to 5mbar, continue 30-40 minute, after goods are taken out, hang in drying oven, be cured;
5th, carry out warm air drying again by after the metal distilled water cleaning after differential arc oxidation process, thus obtain final magnesium alloy product.
2. one kind utilizes the preparation-obtained MB3 magnesium alloy product of the differential arc oxidation treatment method described in claim 1.
CN201210294614.6A 2012-08-17 2012-08-17 Micro-arc oxidation surface treatment method and product prepared by same CN102808210B (en)

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CN103147109A (en) * 2013-03-26 2013-06-12 西北工业大学 Method for sealing aluminum alloy micro-arc oxidation film layer
CN103421997B (en) * 2013-08-30 2015-12-02 山东大学 A kind of degradable Mg-Zn-Si-Ca magnesium base bioceramic compound implant material and preparation method thereof
CN103469280B (en) * 2013-09-24 2016-05-11 重庆研镁科技有限公司 Magnesium alloy differential arc oxidation electrolyte and utilize the technique of this electrolyte to the processing of Mg alloy surface black ceramic
CN103526251B (en) * 2013-10-15 2016-08-17 北京星航机电装备有限公司 A kind of preparation method of the differential arc oxidation film layer with photo-catalysis function
CN104651908B (en) * 2013-11-25 2017-09-29 中国兵器科学研究院宁波分院 The preparation method and method for sealing of a kind of Mg alloy surface ceramic film
CN104131324A (en) * 2014-08-12 2014-11-05 广西玉柴机器股份有限公司 Aluminum alloy piston for internal combustion engine
CN106112818A (en) * 2016-06-29 2016-11-16 重庆铁马工业集团有限公司 A kind of metallic element decontamination process
CN107779930A (en) * 2016-08-31 2018-03-09 昆山汉鼎精密金属有限公司 The surface decorating method and its products formed of magnesium alloy encapsulated products
CN106521602B (en) * 2016-10-25 2018-11-20 中国兵器科学研究院宁波分院 The preparation method of Mg alloy surface composite ceramics film layer
CN107904647A (en) * 2017-11-30 2018-04-13 北京石油化工学院 A kind of Micro-arc Oxidized Ceramic Coatings on Magnesium Alloy hole sealing agent and method for sealing

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