EP0677596A1 - Procede de production d'un revetement en ceramique oxydee - Google Patents
Procede de production d'un revetement en ceramique oxydee Download PDFInfo
- Publication number
- EP0677596A1 EP0677596A1 EP94929654A EP94929654A EP0677596A1 EP 0677596 A1 EP0677596 A1 EP 0677596A1 EP 94929654 A EP94929654 A EP 94929654A EP 94929654 A EP94929654 A EP 94929654A EP 0677596 A1 EP0677596 A1 EP 0677596A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- coating
- sol
- producing
- compound
- oxide ceramic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
Links
- 238000000034 method Methods 0.000 title claims abstract description 38
- 239000011224 oxide ceramic Substances 0.000 title claims abstract description 15
- 229910052574 oxide ceramic Inorganic materials 0.000 title claims abstract description 15
- 238000005524 ceramic coating Methods 0.000 title abstract 4
- 238000000576 coating method Methods 0.000 claims abstract description 19
- 239000011248 coating agent Substances 0.000 claims abstract description 16
- 150000003377 silicon compounds Chemical class 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 13
- 150000002736 metal compounds Chemical class 0.000 claims description 8
- 239000000919 ceramic Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 238000005507 spraying Methods 0.000 claims description 7
- -1 alkoxide compound Chemical class 0.000 claims description 5
- 238000007590 electrostatic spraying Methods 0.000 claims description 5
- 230000005855 radiation Effects 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000005245 sintering Methods 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 abstract description 10
- 238000003980 solgel method Methods 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 3
- 238000005240 physical vapour deposition Methods 0.000 abstract description 2
- 238000005229 chemical vapour deposition Methods 0.000 abstract 1
- 238000001704 evaporation Methods 0.000 abstract 1
- 238000010304 firing Methods 0.000 abstract 1
- 229910000765 intermetallic Inorganic materials 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- 239000012808 vapor phase Substances 0.000 abstract 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- 238000001354 calcination Methods 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 229940046892 lead acetate Drugs 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000005686 electrostatic field Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- VTCHZFWYUPZZKL-UHFFFAOYSA-N 4-azaniumylcyclopent-2-ene-1-carboxylate Chemical compound NC1CC(C(O)=O)C=C1 VTCHZFWYUPZZKL-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910009253 Y(NO3)3 Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000004075 acetic anhydrides Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009503 electrostatic coating Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 108010025899 gelatin film Proteins 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000001947 vapour-phase growth Methods 0.000 description 1
- BXJPTTGFESFXJU-UHFFFAOYSA-N yttrium(3+);trinitrate Chemical compound [Y+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O BXJPTTGFESFXJU-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
- C23C18/1254—Sol or sol-gel processing
Definitions
- the present invention relates to a process for producing oxide ceramics film or membrane using, as a starting material, a solution or a sol of a metal compound.
- Oxide ceramics films have contributed to the development of various industries by utilizing their characteristics as functional materials such as heat-resistant coatings, abrasion-resistant coatings and reflection-preventive films, ultraconductive materials, ion conductive materials, electron materials such as capacitor and memory materials, and sensors and actuators utilizing a piezoelectrical property and pyroelectrical property.
- the formed gel may shrink and crack as drying proceeds. This is because the boundary between a gel skeleton (solid), a solvent (liquid) and air (gas) is formed on the surface layer of the object in the course of drying so that capillary action of pulling the gel skeleton into a pore is generated. Against this action, the inside of the gel tries to maintain a constant volume. Thus, when the tension of the surface layer is greater than the strength of the gel skeleton, the surface layer may crack, and when this difference is extremely large, the gel structure may be destroyed.
- the object of the present invention is to provide a uniform film, without cracking, by electrostatic spraying a solution to form fine particles to thereby be vaporized between a spraying portion and an object to be treated so that a gel film substantially free from solvent molecules is formed on the surface of the object, whereby the generation of the capillary action defined by the formula (I) is prevented.
- the object of the present invention is to form a thick film by a one-pass process and to remarkably raise productivity.
- a process for producing an oxide ceramics film characterized by electrostatic spraying of an alcohol solution, an aqueous solution or a sol of a metal compound or a silicon compound, then coating the resulting sprayed product on the surface of an object to be treated to form a film having a uniform thickness, followed by calcinating so that a ceramics film is formed on the surface of the object.
- the present invention can be broadly classified into three processes for achieving the above-described objects.
- the first process comprises the preparation of a starting solution.
- Metal compounds or silicon compounds which are the supply source of constituent elements are required to be dissolved in a solvent and desirably have a low vapor pressure (for example, 60 mmHg or less).
- alkoxides such as Si(OC2H5)4 and Al(OC3H7)3, metal acetyl acetates such as In(COCH2COCH3), metal carboxylates such as Pb(CH3COO)2 and Y(C17H35COO)3, and nitrates such as Ni(NO3)2 and Y(NO3)3.
- the starting materials per se have a high vapor pressure, they can be used in the present invention, provided that they can be converted to compounds having a low vapor pressure as the result of a reaction in a solution.
- alkoxide compounds are suitable, because if they are used with a small amount of water, they are converted to a high molecular weight substance through hydrolysis and polycondensation reaction in a solution.
- Solvents used in the present invention are required to dissolve the above-described metal compounds and silicon compounds, and desirably have a low specific heat and a high vapor pressure.
- solvents include ethyl alcohol, methyl alcohol, isopropyl alcohol and dimethoxyethane.
- compounds having a hydroxyl group having a high infrared absorption are more desirable because the vaporization thereof can be accelerated by irradiation with infrared radiation.
- the mixing of the above-described metal compound or silicon compound with a solvent can be effected by using an optional process, if it is desired to prevent a reaction with water in the air, the mixing is desirably effected in an atmosphere of dried nitrogen or dried argon.
- a stabilizer chelating agent
- examples of the stabilizer include diethanolamine and acetylacetone.
- a viscosity regulator an acid or an alkali depending upon the purpose of use thereof.
- the second process of the present method comprises a coating process by electrostatic spraying.
- an earthed or grounded object to be treated is used as an anode and a solution spraying unit is used as a cathode.
- a high negative electric voltage is applied to the cathode to form an electrostatic field between these two electrodes, and fine negatively charged particles are sprayed to effectively coat the opposite electrode, i.e., the object to be treated.
- the high voltage is preferably within a range of -30 to -120 kV, more preferably within a range of -30 to -70 kV.
- the distance between the two electrodes is preferably 5 to 40 cm, more preferably 10 to 30 cm.
- the surface to be treated In order to ground an object to be treated, the surface to be treated is required to at least have some electrical conductivity.
- the shape of the object is not severely restricted. Even if the object has a curved surface, a uniform film can be formed.
- the surface to be treated is desirably highly wettable with a sol. If it is not so wettable, a surface treatment may be applied to the surface.
- a surface treatment may be applied to the surface.
- objects to be treated mention may be made of various metals such as iron and copper, conductive glass and quartz glass having platinum deposited thereon.
- the vaporization of solvent particles can be accelerated by irradiating infrared radiation or microwaves between electrodes.
- Infrared irradiation generation units are not particularly limited.
- a type wherein irradiation from an infrared radiation lamp is made parallel by a gold mirror can be used.
- the output of the microwave is not particularly limited. However, it is preferably 500 to 3000W, more preferably, 1000 to 2000W.
- the third process of the present process comprises calcinating an object to be treated.
- the calcinating can be effected in the air, nitrogen atmosphere or in vacuo.
- the calcinating temperature differs depending upon the kind of ceramics.
- the desired ceramics can be obtained preferably around 400 to 1200°C.
- a temperature elevation and lowering process is desirably controlled, for example, by a temperature controller.
- titanic lead zirconate ceramics film on a stainless steel surface.
- Lead (II) acetate trihydrate (produced by Wako Junyaku Industry K.K., guaranteed reagent) was thermally dried at 120°C in vacuo for 3 hours to obtain anhydrous lead acetate. 64.9g of the product obtained was added to the solution prepared above taking care not to cause solidification. At this point, lead acetate was still undissolved. Further, 40g of distilled water diluted with isopropyl alcohol was added dropwise thereto with stirring, whereby lead acetate was completely dissolved to form a uniform sol. The sol obtained was used as a sol for coating.
- a plate made of stainless 304 (10 cm ⁇ 10 cm ⁇ 1.5 mm thickness) was thermally treated at 1050°C in vacuo for one hour, and the treated product was then subjected to mirror surface polishing. The resulting product was used as an object to be treated.
- the electrostatic spraying was conducted by an electrostatic coating device ESG-110 model manufactured by Iwata Toso K.K.
- the coating compound spouting rate was controlled to 1 ml/sec and air pressure for spraying was controlled to 3 kgf/cm2.
- a voltage of -60 kV was applied to a needle electrode in an electrostatic ionizing portion.
- the distance between the stainless plate, the object to be treated and the coating device was kept at 22 cm and the coating device was scanned from right to left at the speed of 20 cm/sec to effect electrostatic spray coating. In order to thicken a film thickness, this scanning can be repeated several times.
- the film thickness after calcinating by one coating was about 0.35 ⁇ m.
- the stainless plate coated by three scans was allowed to stand for about 2 minutes to dry. Thereafter, the dried plate was placed into an electric furnace (muffle furnace AMF-20-2P, manufactured by Asahi Rika Seisakusho). The temperature of the furnace was elevated to 600°C at the rate of 15°C/min, the furnace was kept at that temperature for 1 hour, and thereafter, was allowed to stand for cooling. By this method, a uniform fine titanic lead zirconate film free from cracks was obtained. A perovskite structure inherent to this compound was confirmed by X-ray diffraction.
- the film thickness after calcinating was determined by two methods: a method utilizing an interference band generated by infrared radiation and a method utilizing a weight difference of the stainless plate before and after coating. The results were both 1.05 ⁇ m.
- an oxide ceramics film can be readily produced on the surface of an object to be treated without causing cracking. Further, the process has a high coating efficiency, can be applied to a curved surface and employs a relatively low sintering temperature. Thus, the present process can greatly contribute to improvements of processes for producing an oxide ceramics film.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Ceramic Engineering (AREA)
- Chemically Coating (AREA)
- Oxygen, Ozone, And Oxides In General (AREA)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28029193A JPH07173634A (ja) | 1993-10-14 | 1993-10-14 | 酸化物系セラミックス膜の製造方法 |
| JP280291/93 | 1993-10-14 | ||
| PCT/JP1994/001718 WO1995010640A1 (fr) | 1993-10-14 | 1994-10-13 | Procede de production d'un revetement en ceramique oxydee |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0677596A4 EP0677596A4 (fr) | 1995-08-23 |
| EP0677596A1 true EP0677596A1 (fr) | 1995-10-18 |
Family
ID=17622942
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP94929654A Ceased EP0677596A1 (fr) | 1993-10-14 | 1994-10-13 | Procede de production d'un revetement en ceramique oxydee |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0677596A1 (fr) |
| JP (1) | JPH07173634A (fr) |
| WO (1) | WO1995010640A1 (fr) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102007030585A1 (de) * | 2007-06-27 | 2009-01-02 | Siemens Ag | Verfahren zum Erzeugen einer keramischen Schicht auf einem Bauteil |
| US20200161047A1 (en) * | 2017-04-19 | 2020-05-21 | Advanced Technology & Materials Co., Ltd. | Method for preparing rare earth permanent magnet material |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4998732A (fr) * | 1973-01-29 | 1974-09-18 | ||
| JPS5191949A (en) * | 1975-02-12 | 1976-08-12 | Surariitoryono tosohoho | |
| EP0167088B1 (fr) * | 1984-07-06 | 1989-12-27 | Peter Dipl.-Ing. Ribnitz | Procédé et installation pour le revêtement intérieur d'un objet creux |
| JPS63277770A (ja) * | 1987-05-09 | 1988-11-15 | Nippon Soda Co Ltd | 超電導セラミックス薄膜形成用組成物および超電導セラミックス薄膜の製造方法 |
| JPS63291665A (ja) * | 1987-05-21 | 1988-11-29 | Nisshin Steel Co Ltd | 耐指紋性、耐摩耗性に優れたステンレス鋼板およびその製造方法 |
| JP3257815B2 (ja) * | 1992-03-04 | 2002-02-18 | 積水化学工業株式会社 | 金属酸化物被覆体の製造方法 |
| JPH06137805A (ja) * | 1992-10-27 | 1994-05-20 | Matsushita Electric Ind Co Ltd | ひずみゲージおよびその製造方法 |
-
1993
- 1993-10-14 JP JP28029193A patent/JPH07173634A/ja active Pending
-
1994
- 1994-10-13 WO PCT/JP1994/001718 patent/WO1995010640A1/fr not_active Ceased
- 1994-10-13 EP EP94929654A patent/EP0677596A1/fr not_active Ceased
Non-Patent Citations (2)
| Title |
|---|
| No further relevant documents disclosed * |
| See also references of WO9510640A1 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102007030585A1 (de) * | 2007-06-27 | 2009-01-02 | Siemens Ag | Verfahren zum Erzeugen einer keramischen Schicht auf einem Bauteil |
| US20200161047A1 (en) * | 2017-04-19 | 2020-05-21 | Advanced Technology & Materials Co., Ltd. | Method for preparing rare earth permanent magnet material |
Also Published As
| Publication number | Publication date |
|---|---|
| WO1995010640A1 (fr) | 1995-04-20 |
| EP0677596A4 (fr) | 1995-08-23 |
| JPH07173634A (ja) | 1995-07-11 |
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