CN1138023C - Cathode micro arc electrodepositing method for preparing oxide ceramic coating - Google Patents
Cathode micro arc electrodepositing method for preparing oxide ceramic coating Download PDFInfo
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- CN1138023C CN1138023C CNB011185414A CN01118541A CN1138023C CN 1138023 C CN1138023 C CN 1138023C CN B011185414 A CNB011185414 A CN B011185414A CN 01118541 A CN01118541 A CN 01118541A CN 1138023 C CN1138023 C CN 1138023C
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Abstract
The present invention relates to a coating technology of surface coating layers, and provides a cathode micro arc electrodepositing method for preparing oxide ceramic coating layers. The cathode micro arc electrodepositing method comprises the steps that an insulation film is prepared on the surface of a test sample in advance; the test sample is used as a cathode in anhydrous alcohol containing metal salts, water or an ethanol solution containing water, and a computer is used for continuously controlling pulse voltage and time to carry out electrodeposition. The coating technology not only can be used to obtain single metal oxide ceramic coating layers and composite metal oxide ceramic coating layers but also can be used to obtain multiple metal oxide ceramic coating layers with different components and compositional gradient. Besides, the coating technology has the advantages of simple operation technology and easy automation.
Description
The present invention relates to the top coat paint-on technique, particularly a kind of cathode technique method for preparing multiple oxide ceramic coating belongs to International Classification of Patents C25D9/08.
The method that is used at present preparing oxide ceramic coating both at home and abroad mainly contains physical vapor deposition (PVD), chemical vapor deposition (CVD) and plasma spraying method etc.Utilize PVD, CVD technology can obtain various oxide ceramic coatings, and coating quality height, but because it is a kind of gas-phase reaction deposition technique, therefore often need the air pressure control of higher temperature, strictness etc. in the deposition process, its preparation technology will be subjected to the influence of the geometrical dimension and the shape of reaction chamber, and the apparatus expensive that this technology adopts, the use cost height.These shortcomings have all limited this The Application of Technology.As long as plasma spraying method has that technological process is stable, easy handling, spray efficiency advantages of higher, and strict red-tape operati parameter, just can obtain the coating of favorable reproducibility, and method is economical and practical.But because the related parameter of technological process is many, so the difficult control of the quality of gained coating, and the performance of the coating that is obtained is not high.The common drawback of these methods is to be difficult for obtaining on complex-shaped workpiece the uniform coating of thickness.
Utilized electrochemical deposition technique to prepare the oxide ceramic coating technology in the last few years and receive people's concern day by day, it has following advantage:
1. the composition of coating, thickness and structure can be controlled by regulating electrochemical parameter easily;
2. because electrode is a good conductor, and settling is very high oxide compound of resistance value or oxyhydroxide, sedimentary position is suppressed further deposition because of resistance value is high, deposition forwards to and is not deposited or carry out at position that settled layer is thin, this feasible deposition is not subjected to the restriction of workpiece shape, can obtain even, complete coating on the workpiece of complicated shape;
3. can deposit method economy, easy at a lower temperature.
For this reason, people's research and utilization differential arc oxidization technique obtains oxide ceramic coating, has proposed plasma as Chinese patent 95114880 and has strengthened electrochemical surface potteryization method and product.Differential arc oxidation (MAO) is to grow up on the basis of anodizing technology, can on metallic matrix, obtain the fine and close oxide compound of one deck by anodic oxidation, this layer oxide compound is a layer insulating in electric field, when this insulation layer has certain thickness, apply suitable voltage the breakdown phenomenon of insulation layer can take place, occurred putting the arc phenomenon when puncturing, utilized and put the energy that arc produces and on matrix, to obtain the high-quality oxide coating of one deck.But this technology only is applicable to the valve metal (as Al, Mg) and the alloy thereof that can produce the anodic oxidation phenomenon, and can only obtain the corresponding oxide ceramic coating of this metal, therefore makes this The Application of Technology be restricted.
A kind of deposition-thermal decomposition sintering oxide film method that proposes in the Chinese patent 93100181, although can utilize the cathodic electrochemical deposition method to obtain various sulls, and matrix is unrestricted.But owing to what obtain in the deposition process is oxyhydroxide or other compound, need after deposition, make it change oxide compound into by sintering, and in the sintering process because the sedimental contraction that the volatilization of some material causes easily causes the cracking of produced film, therefore can only be used to obtain film.And the hardness of the film that obtains, density are not fine.
The objective of the invention is to advantage in conjunction with differential arc oxidization technique and cathodic electrochemical deposition technology, a kind of technology of cathode micro arc electrodepositing oxide ceramic coating is proposed, not only can obtain single metal oxide ceramic coating in various metallic surfaces, and can obtain the multilevel oxide of complex metal oxides, heterogeneity and the ceramic coating of component gradient, and the operating procedure of this technology is simple, is easy to automatization.
The present invention at first adopts solution dipping method, sample is heated to 400-1000 ℃, taking out the back immerses in the 0.05-0.3M aqueous metal salt rapidly, treat to take out and dry up after the sample cooling, cyclical operation 10-30 time, at the prefabricated one deck insulation oxide of specimen surface ceramic membrane, again with in the molten dried dehydrated alcohol of metal-salt or water or the aqueous ethanolic soln, the solution that is mixed with concentration and is 0.01-0.2M is as electrolytic solution, with the sample of prefabricated film as negative electrode, sample is applied pulsed voltage, the parameter area of pulsed voltage is that base value voltage is between the 0-100 volt, crest voltage is between the 100-1000 volt, and frequency is between 50-1000Hz, and dutycycle is between 10%-50%, deposit and after 1-12 hour sample is taken out, heated 30-120 minute down in 500-1000 ℃ in inert atmosphere dry back, to remove the trace carbon of surface deposition, can obtain oxide ceramic coating.
Metal-salt among the present invention can be nitrate or carbonate or muriate, and electrolytic solution can be used the metal-salt preparation of Zr, Al, Ce, Y, Ta, Ti, Ca, Mg, Fe, Zn, Pb, Ni, Hf, La, Pd, Co, Cr, Sn element.Electrolytic solution can also can be regulated by the metal-salt preparation of two or more element and the ratio of various metal-salts by a kind of metal-salt preparation of element.Sample can be in different electrolytic solution cyclic deposition.In deposition process, can continuously change the ratio of various metal-salts in the electrolytic solution.
The present invention has the following advantages:
1. the micro-arc discharge phenomenon owing at the prefabricated one deck insulation film of sample surfaces, when the sample in the electrolytic solution is applied certain voltage, can take place in the present invention like this on film.With this sample is negative electrode, is electrolytic solution with the dehydrated alcohol of metal-salt or water or aqueous ethanolic soln, the energy that in negative electrode generation galvanic deposit, utilizes microplasma with sample on sedimentary metallic compound be converted into the oxide ceramic layer of superior performance.Because micro-arc discharge preferentially takes place in the thin spot of film, and preferentially forms oxide ceramics at this place, this place's resistance is increased, micro-arc discharge is transferred to other thin spot then.Consequently micro-arc discharge shifts automatically at sample surfaces, causes the oxide ceramic layer homogenizing and constantly thickens.
2. the present invention can obtain various oxide ceramic coatings.When having only a kind of metal-salt of element in the electrolytic solution, can obtain single metal oxide ceramic coating; When containing two or more metal element salt in the electrolytic solution, can obtain the complex metal oxides ceramic coating, and the ratio of regulating various metal-salts in the electrolytic solution can obtain the complex metal oxides ceramic coating of heterogeneity; When cyclic deposition in different electrolytic solution, can obtain the multiple layer metal oxide ceramic coating of heterogeneity; When changing the ratio of each metal-salt in the electrolytic solution continuously, can obtain the complex metal oxides ceramic coating of component gradient.
3. the present invention can control the thickness and the structure of deposited coatings effectively by the parameter and the depositing time of stepless control pulsed voltage, and processing unit is simple, is easy to automatization
Describe the present invention in detail below in conjunction with embodiment:
1. dispose the Zr (NO of 0.1M
3)
46H
2O+7.8wt%Y (NO
3)
35H
2The aqueous solution of O with the mechanical polishing of Fe25Cr5Al alloy sample, is heated to 1000 ℃ with sample, takes out the Zr (NO that the back is immersed 0.1M rapidly
3)
46H
2O+7.8wt%Y (NO
3)
35H
2In the aqueous solution of O, treat to take out and dry up, cyclical operation 20 times after the sample cooling.With the sample after handling is negative electrode, and platinum electrode is an anode, with the Zr (NO of 0.1M
3)
46H
2O+7.8wt%Y (NO
3)
35H
2The aqueous solution of O is electrolytic solution, applies pulsed voltage (base value voltage is 0v, and crest voltage is 100v, and frequency is 100Hz, and dutycycle is 20%), deposits 12 hours, and sample takes out and heated 2 hours in argon gas under 1000 ℃ dry back, promptly obtains ZrO after the cooling
2-15wt%Y
2O
3Composite ceramic coat.
2. dispose the Al (NO of 0.2M
3)
39H
2Zr (the NO of the ethanol solution of O and the aqueous solution and 0.1M
3)
46H
2The ethanol solution of O with the mechanical polishing of Fe25Cr5Al alloy sample, is heated to 800 ℃ with sample, takes out the Al (NO that the back is immersed 0.2M rapidly
3)
36H
2In the aqueous solution of O, treat to take out and dry up, cyclical operation 10 times after the sample cooling.With the sample after handling is negative electrode, and platinum electrode is an anode, with the Al (NO of 0.2M
3)
36H
2The ethanol solution of O is an electrolytic solution, applies pulsed voltage (base value voltage is 20V, and crest voltage is 100V, and frequency is 100Hz, and dutycycle is 30%), deposits 10 hours, puts into the Zr (NO of 0.1M after sample taking-up and the drying again
3)
46H
2In the ethanol solution of O, (base value voltage is 0v, and crest voltage is 200v to apply pulsed voltage, frequency is 100Hz, and dutycycle is 20%), deposit 12 hours, sample takes out and heated 2 hours in argon gas under 1000 ℃ dry back, and promptly obtaining internal layer after the cooling is Al
2O
3Skin is ZrO
2The double-layer ceramic coating.
3. dispose the Ce (NO of 0.05M
3)
36H
2The ethanolic soln that contains 20% water and the aqueous solution of O with the mechanical polishing of Fe25Cr5Al alloy sample, are heated to 600 ℃ with sample, take out the Ce (NO that the back is immersed 0.05M rapidly
3)
36H
2In the aqueous solution of O, treat to take out and dry up, cyclical operation 20 times after the sample cooling.With the sample after handling is negative electrode, and platinum electrode is an anode, with the Ce (NO of 0.05M
3)
36H
2The ethanolic soln that contains 20% water of O is an electrolytic solution, and (base value voltage is 10V, and crest voltage is 300V to apply pulsed voltage, frequency is 200Hz, and dutycycle is 40%), deposit 2 hours, sample takes out and heated 1 hour in argon gas under 800 ℃ dry back, promptly obtains CeO after the cooling
2Ceramic coating.
4. dispose the Zr (NO of 0.1M
3)
46H
2O+7.8wt%Y (NO
3)
35H
2Zr (the NO of the ethanol solution of O and the aqueous solution and 0.1M
3)
46H
2The ethanol solution of O is heated to 1000 ℃ with sample, takes out the Zr (NO that the back is immersed 0.1M rapidly
3)
46H
2O+7.8wt%Y (NO
3)
35H
2In the O aqueous solution, treat to take out and dry up, cyclical operation 20 times after the sample cooling.With the sample after handling is negative electrode, and platinum electrode is an anode, with the Zr (NO of 0.1M
3)
46H
2O+7.8wt%Y (NO
3)
35H
2The O ethanol solution is an electrolytic solution, applies pulsed voltage (base value voltage is 0v, and crest voltage is 100v, and frequency is 100Hz, and dutycycle is 20%), and the sedimentary while splashes into the Zr (NO of 0.1M in electrolytic solution
3)
46H
2The ethanol solution of O deposits 12 hours, and sample takes out and heated 2 hours in argon gas under 1000 ℃ dry back, promptly obtains ZrO after the cooling
2The ZrO that increases gradually from inside to outside of content
2-Y
2O
3The component gradient ceramic coating.
Claims (4)
1, a kind of cathode micro arc electrodepositing method for preparing oxide ceramic coating is characterized in that, sample is heated to 400-1000 ℃, taking out the back immerses in the 0.05-0.3M aqueous metal salt rapidly, treat to take out and dry up after the sample cooling, cyclical operation 10-30 time, at the prefabricated one deck insulation oxide of specimen surface ceramic membrane, again metal-salt is dissolved in the dehydrated alcohol, the solution that is mixed with concentration and is 0.01-0.2M is as electrolytic solution, with the sample of prefabricated film as negative electrode, sample is applied pulsed voltage, deposit after 1-12 hour sample is taken out, heated 30-120 minute down in 500-1000 ℃ in inert atmosphere dry back.
2, the cathode micro arc electrodepositing method of preparation oxide ceramic coating as claimed in claim 1, it is characterized in that, the parameter area of pulsed voltage is that base value voltage is between the 0-100 volt, crest voltage is between the 1000-1000 volt, frequency is between 50-1000Hz, and dutycycle is between 10%-50%.
3, the cathode micro arc electrodepositing method of preparation oxide ceramic coating as claimed in claim 1 is characterized in that, metal-salt can be nitrate or carbonate or muriate.
4, as claim 1, the cathode micro arc electrodepositing method of 3 described preparation oxide ceramic coatings, it is characterized in that electrolytic solution can use Zr, Al, Ce, Y, Ta, Ti, Ca, Mg, Fe, Zn, Pb, Ni, Hf, La, Pd, Co, Cr, the metal-salt preparation of Sn element, electrolytic solution can be by a kind of metal-salt preparation of element, also can regulate by the metal-salt preparation of two or more element and the ratio of various metal-salts, sample can be in different electrolytic solution cyclic deposition, in deposition process, can continuously change the ratio of various metal-salts in the electrolytic solution.
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| CNB011185414A CN1138023C (en) | 2001-05-31 | 2001-05-31 | Cathode micro arc electrodepositing method for preparing oxide ceramic coating |
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| CN1138023C true CN1138023C (en) | 2004-02-11 |
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| JP4045870B2 (en) * | 2002-06-20 | 2008-02-13 | 富士ゼロックス株式会社 | Optical element manufacturing method, electrodeposition liquid used therefor, and optical element manufacturing apparatus |
| CN104911663B (en) * | 2012-05-10 | 2017-04-19 | 中国兵器工业第五九研究所 | Durable surface coating layer preparation method and system |
| CN104372394A (en) * | 2014-07-03 | 2015-02-25 | 西安工业大学 | Preparation method for oxide ceramic layer |
| CN104562128B (en) * | 2015-01-09 | 2017-10-03 | 西安工业大学 | A kind of method for preparing thermal protection ceramic layer on metal or metallic composite surface |
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| CN105420774A (en) * | 2015-11-03 | 2016-03-23 | 中国第一汽车股份有限公司 | Method for preparing nano cerium oxide coating on metal carrier |
| CN105441999A (en) * | 2015-11-03 | 2016-03-30 | 中国第一汽车股份有限公司 | Method for preparing nanometer lanthanum oxide coating on metal carrier |
| CN108147831B (en) * | 2016-12-06 | 2020-06-12 | 航天特种材料及工艺技术研究所 | Preparation method of C/C composite material high-temperature oxidation-resistant coating |
| CN106480482B (en) * | 2016-12-15 | 2018-12-18 | 河海大学常州校区 | A kind of cathode surface nanosecond pulse plasma prepares the solution and preparation method of catalytic nanometer perforated membrane |
| CN106801241A (en) * | 2017-02-13 | 2017-06-06 | 广东飞翔达科技有限公司 | The device and method of a kind of ceramic protective coating of generation on metal parts |
| CN107557836B (en) * | 2017-09-07 | 2019-11-05 | 西北工业大学 | TiAl alloy surface cathode micro arc plasma body electrolytic deposition prepares CeO2-Al2O3The method of composite ceramic layer |
| CN111378970B (en) * | 2020-04-26 | 2021-07-13 | 西安交通大学 | Method for preparing high-frequency electric knife insulating coating based on micro-arc oxidation method |
| CN111676499A (en) * | 2020-07-30 | 2020-09-18 | 华南理工大学 | Hydrogen-resistant coating based on cathode plasma electrolytic deposition and preparation method thereof |
| CN112647106A (en) * | 2020-10-29 | 2021-04-13 | 西安交通大学 | Method for preparing zirconia-based ceramic coating by electrolyzing stainless steel surface catholyte phase plasma |
| CN113430613A (en) * | 2021-06-17 | 2021-09-24 | 西安交通大学 | Method for preparing ceramic coating on inner surface and outer surface of complex special-shaped component |
| CN115745644B (en) * | 2022-11-14 | 2023-08-22 | 航天特种材料及工艺技术研究所 | Carbon fiber toughened ceramic matrix composite material and preparation method thereof |
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