CN1040345C - Electro-chemical deposition-thermal decomposition method for sintering oxide film - Google Patents
Electro-chemical deposition-thermal decomposition method for sintering oxide film Download PDFInfo
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- CN1040345C CN1040345C CN93100181A CN93100181A CN1040345C CN 1040345 C CN1040345 C CN 1040345C CN 93100181 A CN93100181 A CN 93100181A CN 93100181 A CN93100181 A CN 93100181A CN 1040345 C CN1040345 C CN 1040345C
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- film
- oxide film
- pyrolysis
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Abstract
At present, techniques for preparing oxide films at home and abroad have respective advantages, but most of the techniques have a quantity of defects, such as high cost, cockamamie technology, difficult coating of workpieces with complicated shapes and large sizes, etc. Consequently, the popularization and the application of the existing coating techniques are all limited to a certain extent. For the reason, the present invention discloses novel electrochemical deposition-thermolysis burning technology, and realizes the preparation for various oxide films. The present invention not only overcomes a plurality of defects of a PVD technique, a CVD technique and other techniques, but also has a quantity of advantages of simple technology, economy, good reliability, easy automation, etc. Moreover, the present invention is also suitable for a plurality of technical fields, such as metallurgy, machinery, electron, optics, etc.
Description
The invention belongs to the top coat paint-on technique, it relates generally to the preparation of various sulls.
The method that is used for preparing sull at present mainly contains chemical vapor deposition (CVD), sol-gel (Sol-Gel) and nitrate pyrolysis.Though utilize the CVD technology can prepare nearly all useful sull, but because it is a kind of gas-phase reaction deposition technique, therefore often need higher temperature, the air pressure of strictness and suitable gas velocity in the deposition process, so preparation technology not only will be subjected to the restriction of reaction system, and to be subjected to the influence of the geometrical dimension and the geometrical shape of reaction chamber; In addition, its deadly defect is sedimentation velocity extremely slow (generally at 0.1～0.3 μ m/hr), and this has just limited its application (the Liu Guang vermachen is translated, J.L.Vossen, W.Kem work, processing film technology, China Machine Press, 1987) in some aspects.The Sol-Gel technology is a kind of colloid chemistry paint-on technique, though can be also extensive relatively with the sull of its preparation, but, owing to when carrying out paint-on technique, need at first prepare hydroxide sol, and the pH value of solution requires very tight, so its disadvantage is to be difficult to obtain the uniform film (E.Lang of thickness, ed.Coating forHigh Temperature Applications, Applied Science Pub.Lishers, London and NewYouk, 1983, P33, P169).The nitrate pyrolysis method is the method (M.Landkofetal, Corrosion, Vol.41,344,1985) that a kind of principle of utilizing some metal nitrate can at high temperature be decomposed into corresponding oxide prepares sull; Though this technology is extremely simple, for complex-shaped workpiece and inapplicable, in addition, this technology also is difficult to obtain all films of even consistent appearance of thickness.Therefore, the paint-on technique of existing sull is not that sedimentation velocity is extremely slow, is exactly that operation is numerous and diverse or be difficult to obtain the film of uniformity, so they are not the most practical sull paint-on technique.
Purpose of the present invention promptly is to overcome the deficiency of above-mentioned various paint-on technique, utilizes the electrode reaction in the electrochemical deposition, obtains deposited film on negative electrode, then it is placed hot environment, and making it pyrolysis becomes corresponding sull.Like this, it has not only overcome many shortcomings of existing technology, and extremely simple, economical, reliable.In addition, utilize this technology not only can prepare various useful sulls, and can obtain the film of uniformity by the suitable control of processing parameter fully.
Electrochemical deposition of the present invention---the method for pyrolysis sintering oxide film, adopt electrochemical deposition and pyrolysis to fire two processes, being about to metal-salt is dissolved in the dehydrated alcohol, to wait to be coated with workpiece as negative electrode, under certain voltage, carry out galvanic deposit, the deposited film that obtains pyrolysis under a certain temperature, can obtain required sull then.Utilize this method can prepare all useful sulls.As: Al
2O
3, Cr
2O, MgO, CaO, Fe
2O
3, Fe
3O
4, NiO, CoO, SnO
2, ZnO, PbO, Y
2O
3, CeO
2, Ce
2O
3, La
2O
3, HfO
2, Pd
2O
5, Ta
2O
5Or the like.
Electrochemical deposition of the present invention---the method for pyrolysis sintering oxide film can be with metal-salt dehydrated alcohol or dehydrated alcohol+1～10%VolH
2Being mixed with concentration among the O is 10
-4～10
-1The solution of M, solution temperature are room temperature, then under the voltage of 5～150V/cm, cathodic deposition 15～600 seconds, with post-depositional sample take out, drying, afterwards again at air in 200～1000 ℃ of following pyrolysis 30～120 minutes, can obtain required sull like this.
The quality of film can realize by the control to film thickness.When film thick during less than 0.2 μ m, the general even flawless of film; When film thickness during greater than 0.5 μ m, film mostly is segmentation crack in various degree.For the crackle in the film, can adopt the additive ethyl cellulose that in electrolyzer, adds trace usually to be eliminated, its content generally is controlled at 0.1～0.5% of metal dissolved salt concentration and gets final product, the film thickness that obtains thus is generally below 0.5 μ m, therefore as needing the preparation thick film then can not adopt additive, maybe can adopt the operation of cyclic deposition, sedimentary again repeatable operation after promptly firing.
Adopt the present invention can also prepare many composite oxide films, as: Al
2O
3-Y
2O
3, Al
2O
3-CeO
2, ZrO
2-Y
2O
3, ZrO
2-CeO
2Deng, this moment, the composition of plating bath can be according to the requirement of thin film composition, make the solution metal salt ionic concentration than with film in composition than identical.
Adopt the present invention can also prepare multilevel oxide film (comprising with a kind of and different sulls), promptly by above-mentioned described technology, deposit-fire, the cyclical operation of deposit-firing again just can obtain the multilevel oxide film.
The present invention is described in detail by embodiment with reference to the accompanying drawings.
The Y that Fig. 1 makes for the embodiment of the invention 1
2O
3The scanning electron microscope of film surface appearance.
The CeO that Fig. 2 makes for the embodiment of the invention 2
2The scanning electron microscope of film surface appearance.
The Al that Fig. 3 makes for the embodiment of the invention 3
2O
3The scanning electron microscope of film surface appearance.
The scanning electron microscope of the MgO film surface appearance that Fig. 4 makes for the embodiment of the invention 4.
The ZrO that Fig. 5 makes for the embodiment of the invention 5
2The scanning electron microscope of film surface appearance.
The SnO that Fig. 6 makes for the embodiment of the invention 6
2The scanning electron microscope of film surface appearance.
The ZnO that Fig. 7 makes for the embodiment of the invention 7
2The scanning electron microscope of film surface appearance.
The scanning electron microscope of the PbO film surface appearance that Fig. 8 makes for the embodiment of the invention 8.
Embodiment 1:
Y (the NO of preparation 0.05M
3)
37H
2The ethanol solution of O is made negative electrode with 321 stainless steel samples of electropolishing then, and pure aluminum plate is made anode, the strength of electric field deposit of 15V/cm 15 seconds, fires in air under 300 ℃ 30 minutes after the drying again, promptly gets Y after the cooling
2O
3Film, its pattern is seen Fig. 1.
Embodiment 2:
Ce (the NO of preparation 0.005M
3)
37H
2The ethanol solution of O is made negative electrode with 321 stainless steel samples of electropolishing then, and pure aluminum plate is made anode, the strength of electric field deposit of 15V/cm 15 seconds, fires in air under 300 ℃ 300 minutes after the drying again, promptly gets CeO after the cooling
2Film, its pattern is seen Fig. 2.
Embodiment 3:
The AlCl of preparation 0.005M
3Ethanol solution, then 321 stainless steel samples of electropolishing are made negative electrode, pure aluminum plate is made anode, the strength of electric field deposit of 100V/cm 15 seconds, fires in air under 500 ℃ 300 minutes after the drying again, promptly gets Al after the cooling
2O
3Film, its pattern is seen Fig. 3.
Embodiment 4:
The MgCl of preparation 0.05M
26H
2The ethanol solution of O is made negative electrode with 321 stainless steel samples of electropolishing then, and pure aluminum plate is made anode, the strength of electric field deposit of 15V/cm 15 seconds, fired in air under 300 ℃ 30 minutes after the drying again, promptly get the MgO film after the cooling, its pattern is seen Fig. 4.
Embodiment 5:
The ZrOCl of preparation 0.005M
28H
2The ethanol solution of O is made negative electrode with 321 stainless steel samples of electropolishing then, and pure aluminum plate is made anode, the strength of electric field deposit of 15V/cm 300 seconds, fires in air under 300 ℃ 30 minutes after the drying again, promptly gets ZrO after the cooling
2Film, its pattern is seen Fig. 5.
Embodiment 6:
The SnCl of preparation 0.05M
22H
2The ethanol solution of O is made negative electrode with 321 stainless steel samples of electropolishing then, and pure aluminum plate is made anode, the strength of electric field deposit of 15V/cm 60 seconds, fires in air under 300 ℃ 30 minutes after the drying again, promptly gets SnO after the cooling
2The film (see figure 6).
Embodiment 7:
The ZnCl of preparation 0.05M
2Ethanol solution, then 321 stainless steel samples of electropolishing are made negative electrode, pure aluminum plate is made anode, the strength of electric field deposit of 15V/cm 300 seconds, fired in air under 300 ℃ 30 minutes after the drying again, promptly get ZnO film after the cooling, its pattern is seen Fig. 7.
Embodiment 8:
Prepare saturated PbAc
23H
2The ethanol solution of O is made negative electrode with 321 stainless steel samples of electropolishing then, and pure aluminum plate is made anode, the strength of electric field deposit of 15V/cm 300 seconds, fired in air under 300 ℃ 30 minutes after the drying again, promptly get the PbO film after the cooling, its pattern is seen Fig. 8.
Adopt the present invention, can prepare the sull of multiple uniformity on demand, and technology is simple, be easy to control, therefore can be widely used in technical fields such as metallurgy, machinery, electronics, optics.
Claims (3)
1, a kind of electrochemical deposition---the preparation method of pyrolysis sintering oxide film is characterized in that adopting electrochemical deposition and pyrolysis to fire two steps, and metal-salt is dissolved in dehydrated alcohol or dehydrated alcohol+1～10%volH
2Among the O, being mixed with concentration is 10
-4～10
-1The solution of M, solution temperature are room temperature, then under the strength of electric field of 5～150V/cm, cathodic deposition 15～600 seconds, with post-depositional sample take out, drying, afterwards again in air in 200～1000 ℃ of following pyrolysis 30～120 minutes.
2, electrochemical deposition as claimed in claim 1---the preparation method of pyrolysis sintering oxide film is characterized in that adopting depositing-firing, deposit-cyclical operation of firing.
3, electrochemical deposition as claimed in claim 1---the preparation method of pyrolysis sintering oxide film is characterized in that adding micro-cathodic deposition additive ethyl cellulose in plating bath, and its content is 0.1～0.5% of metal-salt content.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93100181A CN1040345C (en) | 1993-01-09 | 1993-01-09 | Electro-chemical deposition-thermal decomposition method for sintering oxide film |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93100181A CN1040345C (en) | 1993-01-09 | 1993-01-09 | Electro-chemical deposition-thermal decomposition method for sintering oxide film |
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| Publication Number | Publication Date |
|---|---|
| CN1089667A CN1089667A (en) | 1994-07-20 |
| CN1040345C true CN1040345C (en) | 1998-10-21 |
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|---|---|---|---|
| CN93100181A Expired - Fee Related CN1040345C (en) | 1993-01-09 | 1993-01-09 | Electro-chemical deposition-thermal decomposition method for sintering oxide film |
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|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1067457A (en) * | 1991-04-08 | 1992-12-30 | Skw金属(英国)有限公司 | Molybdenum parts and manufacture method thereof that plating is crossed |
-
1993
- 1993-01-09 CN CN93100181A patent/CN1040345C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1067457A (en) * | 1991-04-08 | 1992-12-30 | Skw金属(英国)有限公司 | Molybdenum parts and manufacture method thereof that plating is crossed |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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| Publication number | Publication date |
|---|---|
| CN1089667A (en) | 1994-07-20 |
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