CN1928165A - Method for producing arc differential oxide ceramic layer on Mg metal surface - Google Patents
Method for producing arc differential oxide ceramic layer on Mg metal surface Download PDFInfo
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- CN1928165A CN1928165A CN 200610042990 CN200610042990A CN1928165A CN 1928165 A CN1928165 A CN 1928165A CN 200610042990 CN200610042990 CN 200610042990 CN 200610042990 A CN200610042990 A CN 200610042990A CN 1928165 A CN1928165 A CN 1928165A
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- ceramic layer
- oxide ceramic
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Abstract
The process of forming micro arc oxide ceramic layer on the surface of magnesium alloy in high efficiency, low power consumption and high coating performance includes the first connecting the pre-treated magnesium alloy workpiece with the positive pole of great power pulse power source and setting in alkaline electrolyte solution compounded with deionized water and sodium silicate as main material inside an electrolytic bath with cathode of stainless steel, and micro arc oxidizing the surface of the magnesium alloy workpiece with asymmetrical AC pulse voltage in sectional applying mode. The sodium silicate electrolyte system is compounded with Na2SiO3.9H2O 30 g/L, NaOH or KOH 1-20 g/L, KF.2H2O 10-40 g/L, C3H5(OH)3 5-25 g/L, and NaAlO2.H2O or Na3C6H5O7.2H2O 5-50 g/L, and has pH value of 10-13.
Description
Technical field
The present invention relates to the top coat paint-on technique, particularly produce ceramic layer at alloy surface differential arc oxidization.
Background technology
Magnesium is metallic substance (density 1.74g/cm the lightest in the engineering materials
3), it is widely used in fields such as automobile, electronics, aviation with the alloy that elements such as aluminium, zinc, molybdenum, zirconium constitute owing to having excellent physics, mechanical property.(equilibrium potential-2.34V), the natural oxide film on surface is loose porous, can not form good provide protection to matrix, causes the solidity to corrosion of magnesium and alloy thereof very poor, has seriously restricted the application of magnesium alloy in industry-by-industry but the chemical property of magnesium is very active.
Handle the ceramic layer that generates in the metallic surface by differential arc oxidation and have wear-resisting preferably, anti-corrosion, insulating property and good surface appearance, stronger with the bonding force of matrix, utilize differential arc oxidization technique that magnesium alloy is carried out the surface ceramic deposition processing and more and more come into one's own with the technology that improves its wear resistance and corrosion resistance, relevant research work deepens continuously and carries out.But existing differential arc oxidization technique still exists many deficiencies, as install complexity, efficient is low, cost is high, current consumption is big etc.As " China YouSe Acta Metallurgica Sinica ", 2002,12 (3): the complete assembly of the differential arc oxidation of introducing among the 454-457 " magnesium alloy micro-arc oxidization ceramic coating microscopic defect and phase composite " includes high-voltage power supply, stainless steel electrolytic groove, stirring system, circulating cooling system etc., and circulating cooling system is made up of recycle pump, cooling tube and cooling tank, the device structure more complicated; " metal heat treatmet ", 2001, point out high-voltage and a large amount of electric energy of high current density consumption that differential arc oxidation uses among the 1:1-3 " commentary of non-ferrous metal surface by micro-arc oxidation technology ", and limited the working (finishing) area of single workpiece, technical costs is generally higher, only can carry out the production of short run in the laboratory or be used for aviation and industry such as military project, the large-scale industrial application prospect is not expected.In the differential arc oxidation process, the Electric Field Characteristics that is applied to surface of metal electrode has determined the performance and the formation speed of surface ceramic layer.Simultaneously, along with the carrying out of differential arc oxidation process, rete itself again can be to continuing the discharge generation restriction effect.The growth pattern of rete is an ecto-entad, and the therefore initial rete that generates will be positioned at most external at last, and its hardness and outward appearance have determined the hardness and the outward appearance of whole rete.The rete of follow-up generation is positioned at inside, its thickness, porousness, has determined wear-resisting, the corrosion resisting property of whole rete with the bonding force of matrix.Through experimental studies have found that, the conditions at the arc of base metal surface have decisive influence to the performance of final generation rete: arc temperature is high more, density is big more, and the speed of growth of rete is fast more, the surface is even more; But the too high then current consumption of arc temperature increases, and because the process of growth of rete is the venting reaction, and the speed of growth is too fast to be easy to cause avalanche and crackle.Directly influence the conditions at the arc on surface at the added asymmetric pulses magnitude of voltage of the different times of coating growth.
Summary of the invention
The objective of the invention is to improve the efficient that magnesium alloy surface micro-arc oxidation is handled, reduce power consumption, the coating that obtained performance is good.
The present invention adopts following technical scheme:
With pretreated magnesium alloy workpiece and the alkaline electrolyte of putting into the deionized water preparation after the positive pole of the high-power all-wave pulse power is connected based on water glass, electric tank cathode adopts stainless material, adopts asymmetric ac pulse voltage that Mg alloy surface is carried out differential arc oxidation; In the differential arc oxidation process, ac pulse voltage adopts predefined segmentation pressuring method and magnitude of voltage.
Asymmetric alternating-current pulse other electrical parameters except that positive voltage are: frequency 10-700Hz, dutycycle 0.1-30, negative voltage 5-50V.
The proportioning of described water glass system electrolytic solution is:
Na
2SiO
3·9H
2O10： 30g/L，
NaOH or KOH:1～20g/L,
KF·2H
2O： 10～40g/L，
C
3H
5(OH)
3： 5～25g/L，
NaAlO
2H
2O or Na
3C
6H
5O
72H
2O:5～50g/L,
The pH value of solution is between 10～13.
Compared with prior art, because the segmentation pressurization is at the characteristics of differential arc oxidation process self, apply corresponding different magnitude of voltage at the different growth phase of rete, thereby the growth conditions of control rete and the performance of the rete that generates, this has just improved the utilization ratio of electric current, reduced that electric arc shortens the reaction times to generating the destruction of rete greatly in the reaction process.Therefore, the present invention has following advantage:
1. equipment used is simple, easy to operate, production efficiency is high, reduce energy consumption.Added asymmetric alternating-current pulse positive voltage carries out according to pre-designed pressuring method and pressurization numerical value in the differential arc oxidation process, and the time spent is very short, increases work efficiency greatly.Simultaneously since the reaction times short, emit less calories, the device system is not high to the requirement of cooling system.
2. segmentation pressurization can change design according to the expectation to the rete different performance, thereby the rete of acquisition is improved accordingly at aspects such as thickness, hardness, solidity to corrosions.
3. be suitable for using the segmentation pressurization to have a variety of in the electrolytic solution type of magnesium alloy surface micro-arc galvanic deposit ceramic layer, wherein the alkaline electrolyte based on silicate can obtain even, fine and close canescence ceramic layer at Mg alloy surface, and this electrolyte system environmentally safe.
4. use the segmentation pressurization that required good bottom can be provided fast as the further aftertreatment of magnesium alloy.
Embodiment
Embodiment 1
Use AZ91D thixotropic forming magnesium alloy workpiece, this magnesium alloy composition is for containing elements such as aluminium 8.5～9.5%, zinc 0.45～0.90%, manganese 0.17～0.4%, a spot of iron, silicon, copper, nickel, and all the other are magnesium.Use two-way all-wave pulse mao power source, magnesium alloy workpiece is linked to each other with positive source.Whole process flow is: polishing, cleaning, oil removing, differential arc oxidation cleans drying.Electrolyte parameter and other electrical parameters except that positive voltage are as follows:
Na
2SiO
3·9H
2O： 15g/L
NaOH： 2g/L
KF·2H
2O： 13g/L
C
3H
5(OH)
3： 18g/L
NaAlO
2·2H
2O： 5g/L
Frequency: 50Hz
Dutycycle: 10
Negative voltage: 10V
The segmentation pressing technology is designed to: pressurize each 30s at interval 4 times; Make current density remain on 15～20A/dm in interval for the first time
2, make current density remain on 10～20A/dm in interval for the second time
2, make current density remain on 5～15A/dm in interval for the third time
2, the 4th minor tick makes current density remain on 5～10A/dm in the phase
2Time spent 2min, gained thicknesses of layers are 28 μ m, and surperficial macrohardness is 72 (HV
294), surperficial even compact.
Embodiment 2
Use AZ91D thixotropic forming magnesium alloy workpiece, use two-way all-wave pulse mao power source, magnesium alloy workpiece is linked to each other with positive source.Whole process flow, electrolyte parameter and other electrical parameters are with embodiment 1.
The segmentation pressing technology is designed to: pressurize each 60s at interval 4 times; The 1st minor tick makes current density remain on 12～18A/dm in the phase
2, the 2nd minor tick makes current density remain on 10～18A/dm in the phase
2, the 3rd minor tick makes current density remain on 7～10A/dm in the phase
2, the 4th makes current density remain on 5～8A/dm in interval
2Time spent 4min, gained thicknesses of layers are 40 μ m, and surperficial macrohardness is 85 (HV
294), surperficial even compact.
Embodiment 3
Use AZ91D cast magnesium alloys workpiece, use two-way all-wave pulse mao power source, magnesium alloy workpiece is linked to each other with positive source.Technical process, electrolyte parameter and other electrical parameters are with embodiment 1.
The segmentation pressing technology is designed to: pressurize each 30s at interval 4 times; The 1st minor tick makes current density remain on 15～25A/dm in the phase
2, the 2nd minor tick makes current density remain on 15～20A/dm in the phase
2, the 3rd minor tick makes current density remain on 10～15A/dm in the phase
2, the 4th makes current density remain on 5～10A/dm in interval
2Time spent 2min, gained thicknesses of layers are 28 μ m, and surperficial macrohardness is 77 (HV
294), surperficial even compact.
Embodiment 4
Use AZ91D cast magnesium alloys workpiece, use two-way all-wave pulse mao power source, magnesium alloy workpiece is linked to each other with positive source.Technical process such as embodiment 1.Electrolyte parameter and other electrical parameters except that positive voltage are as follows:
Na
2SiO
3·9H
2O 20g/L
NaOH 5g/L
KF·2H
2O 18g/L
C
3H
5(OH)
3 20g/L
Na
3C
6H
5O
7·2H
2O 30g/L
Frequency 600Hz
Dutycycle 5
Negative voltage 20V
The segmentation pressing technology is designed to: pressurize each 90s at interval 5 times; The 1st minor tick makes current density remain on 15～25A/dm in the phase
2, the 2nd minor tick makes current density remain on 10～20A/dm in the phase
2, the 3rd minor tick makes current density remain on 10～15A/dm in the phase
2, the 4th makes current density remain on 8～12A/dm in interval
2, the 5th makes current density remain on 5～10A/dm in interval
2Time spent 7.5min, gained thicknesses of layers are 49 μ m, and surperficial macrohardness is 78 (HV
294), surperficial even compact.
Embodiment 5
Use AZ91D cast magnesium alloys workpiece, use two-way all-wave pulse mao power source, magnesium alloy workpiece is linked to each other with positive source.Technical process such as embodiment 1.Electrolyte parameter and other electrical parameters except that positive voltage are as follows:
Na
2SiO
3·9H
2O： 18g/L
NaOH： 4g/L
KF·2H
2O： 15g/L
C
3H
5(OH)
3： 25g/L
NaAlO
2·2H
2O： 10g/L
Frequency: 700Hz
Dutycycle: 1
Negative voltage: 10V
The segmentation pressing technology is designed to: pressurize each 120s at interval 6 times; The 1st minor tick makes current density remain on 15～25A/dm in the phase
2, the 2nd minor tick makes current density remain on 12～18A/dm in the phase
2, the 3rd minor tick makes current density remain on 6～12A/dm in the phase
2, the 4th makes current density remain on 5～10A/dm in interval
2, the 5th makes current density remain on 5～8A/dm in interval
2, the 6th minor tick makes current density remain on 1～5A/dm in the phase
2Time spent 12min, gained thicknesses of layers are 71 μ m, and surperficial macrohardness is 75 (HV
294), surperficial even compact.
Claims (3)
1, generates the method for arc differential oxide ceramic layer at Mg alloy surface, with pretreated magnesium alloy workpiece and the alkaline electrolyte of putting into the deionized water preparation after the positive pole of the high-power all-wave pulse power is connected based on water glass, it is characterized in that: electric tank cathode adopts stainless material, adopts asymmetric ac pulse voltage that Mg alloy surface is carried out differential arc oxidation; In the differential arc oxidation process, ac pulse voltage adopts predefined segmentation pressuring method and magnitude of voltage.
2, the method at Mg alloy surface generation arc differential oxide ceramic layer according to claim 1, it is characterized in that: asymmetric alternating-current pulse other electrical parameters except that positive voltage are: frequency 10～700Hz, dutycycle 0.1～30, negative voltage 5～50V.
3, the method at Mg alloy surface generation arc differential oxide ceramic layer according to claim 1, it is characterized in that: the proportioning of described water glass system electrolytic solution is:
Na
2SiO
3·9H
2O10： 30g/L，
NaOH or KOH:1～20g/L,
KF·2H
2O： 10～40g/L，
C
3H
5(OH)
3： 5～25g/L，
NaAlO
2H
2O or Na
3C
6H
5O
72H
2O:5～50g/L,
The pH value of solution is between 10～13.
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|---|---|---|---|
| CN 200610042990 CN1928165A (en) | 2006-06-13 | 2006-06-13 | Method for producing arc differential oxide ceramic layer on Mg metal surface |
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|---|---|---|---|
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101275263B (en) * | 2007-12-18 | 2010-08-11 | 华南理工大学 | Voltage step micro-arc oxidation method |
| CN101270495B (en) * | 2008-04-21 | 2010-10-27 | 华南理工大学 | Method for preparing corrosion protection abrasion resistant ceramic coating with alloy surface differential arc oxidization |
| CN101914765A (en) * | 2010-08-31 | 2010-12-15 | 沈阳理工大学 | Method for preparing dark-colored ceramic membranes by chemical conversion-micro-arc oxidation of magnesium alloys |
| CN101701350B (en) * | 2009-11-30 | 2011-02-16 | 哈尔滨工业大学 | Processing method for strengthening surface of MB15 magnesium alloy |
| CN102268711A (en) * | 2011-06-22 | 2011-12-07 | 沈阳理工大学 | Method for preparing biological composite coating on surface of magnesium-based material |
| CN102304739A (en) * | 2011-09-19 | 2012-01-04 | 北京科技大学 | Micro-arc oxidation preparation method of high wear resistant and corrosion resistant self-lubricating ceramic layer and electrolyte thereof |
| CN102367584A (en) * | 2011-09-19 | 2012-03-07 | 北京科技大学 | Metal microarc oxidation electrolyte and method for forming black ceramic coating on metal surface by microarc oxidation |
| CN103320841A (en) * | 2013-05-10 | 2013-09-25 | 上海理工大学 | Formula and application method of magnesium alloy micro-arc oxidation solution |
| CN103628113A (en) * | 2012-08-22 | 2014-03-12 | 中国人民解放军装甲兵工程学院 | Nanometer electrolyte for micro-arc oxidation of magnesium alloy |
| CN104404601A (en) * | 2014-12-19 | 2015-03-11 | 中北大学 | Micro-arc oxidation treatment technology of Mg-Gd-Y-Zr casting magnesium alloy |
| CN105780081A (en) * | 2016-04-25 | 2016-07-20 | 兰州理工大学 | Electrolyte for preparing micro-arc oxidation ceramic composite coating |
| CN105887084A (en) * | 2016-05-12 | 2016-08-24 | 广东省材料与加工研究所 | Method for preparing magnesium alloy composite coating with self-repair function |
| CN105887159A (en) * | 2016-05-12 | 2016-08-24 | 广东省材料与加工研究所 | Method for preparing magnesium alloy composite coating with decorativeness and functionality |
| CN106624675A (en) * | 2017-01-24 | 2017-05-10 | 穆耀钊 | Brake disc or brake drum and preparation method for wear-resisting brake disc or brake drum |
| CN109023481A (en) * | 2018-10-19 | 2018-12-18 | 北京杜尔考特科技有限公司 | Magnesium substrates production method, magnesium substrates with ceramic flame-proof layer and application thereof |
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2006
- 2006-06-13 CN CN 200610042990 patent/CN1928165A/en active Pending
Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101275263B (en) * | 2007-12-18 | 2010-08-11 | 华南理工大学 | Voltage step micro-arc oxidation method |
| CN101270495B (en) * | 2008-04-21 | 2010-10-27 | 华南理工大学 | Method for preparing corrosion protection abrasion resistant ceramic coating with alloy surface differential arc oxidization |
| CN101701350B (en) * | 2009-11-30 | 2011-02-16 | 哈尔滨工业大学 | Processing method for strengthening surface of MB15 magnesium alloy |
| CN101914765B (en) * | 2010-08-31 | 2012-07-04 | 沈阳理工大学 | Method for preparing dark-colored ceramic membranes by chemical conversion-micro-arc oxidation of magnesium alloys |
| CN101914765A (en) * | 2010-08-31 | 2010-12-15 | 沈阳理工大学 | Method for preparing dark-colored ceramic membranes by chemical conversion-micro-arc oxidation of magnesium alloys |
| CN102268711A (en) * | 2011-06-22 | 2011-12-07 | 沈阳理工大学 | Method for preparing biological composite coating on surface of magnesium-based material |
| CN102367584B (en) * | 2011-09-19 | 2014-04-16 | 北京科技大学 | Metal microarc oxidation electrolyte and method for forming black ceramic coating on metal surface by microarc oxidation |
| CN102304739A (en) * | 2011-09-19 | 2012-01-04 | 北京科技大学 | Micro-arc oxidation preparation method of high wear resistant and corrosion resistant self-lubricating ceramic layer and electrolyte thereof |
| CN102304739B (en) * | 2011-09-19 | 2015-06-03 | 北京科技大学 | Micro-arc oxidation preparation method of high wear resistant and corrosion resistant self-lubricating ceramic layer and electrolyte thereof |
| CN102367584A (en) * | 2011-09-19 | 2012-03-07 | 北京科技大学 | Metal microarc oxidation electrolyte and method for forming black ceramic coating on metal surface by microarc oxidation |
| CN103628113A (en) * | 2012-08-22 | 2014-03-12 | 中国人民解放军装甲兵工程学院 | Nanometer electrolyte for micro-arc oxidation of magnesium alloy |
| CN103320841A (en) * | 2013-05-10 | 2013-09-25 | 上海理工大学 | Formula and application method of magnesium alloy micro-arc oxidation solution |
| CN103320841B (en) * | 2013-05-10 | 2015-12-23 | 上海理工大学 | A kind of magnesium alloy differential arc oxidation solution formula and application method thereof |
| CN104404601A (en) * | 2014-12-19 | 2015-03-11 | 中北大学 | Micro-arc oxidation treatment technology of Mg-Gd-Y-Zr casting magnesium alloy |
| CN105780081B (en) * | 2016-04-25 | 2018-12-14 | 兰州理工大学 | Prepare the electrolyte of arc differential oxide ceramic composite coating |
| CN105780081A (en) * | 2016-04-25 | 2016-07-20 | 兰州理工大学 | Electrolyte for preparing micro-arc oxidation ceramic composite coating |
| CN105887084A (en) * | 2016-05-12 | 2016-08-24 | 广东省材料与加工研究所 | Method for preparing magnesium alloy composite coating with self-repair function |
| CN105887159B (en) * | 2016-05-12 | 2018-04-10 | 广东省材料与加工研究所 | One kind has ornamental and functional magnesium alloy preparation method of composite coating concurrently |
| CN105887084B (en) * | 2016-05-12 | 2018-10-30 | 广东省材料与加工研究所 | A kind of magnesium alloy preparation method of composite coating with self-repair function |
| CN105887159A (en) * | 2016-05-12 | 2016-08-24 | 广东省材料与加工研究所 | Method for preparing magnesium alloy composite coating with decorativeness and functionality |
| CN106624675A (en) * | 2017-01-24 | 2017-05-10 | 穆耀钊 | Brake disc or brake drum and preparation method for wear-resisting brake disc or brake drum |
| CN106624675B (en) * | 2017-01-24 | 2018-07-27 | 西安傲博赛制动科技有限公司 | The preparation method and brake disc or brake drum of wear-resisting brake disc or brake drum |
| CN109023481A (en) * | 2018-10-19 | 2018-12-18 | 北京杜尔考特科技有限公司 | Magnesium substrates production method, magnesium substrates with ceramic flame-proof layer and application thereof |
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