EP0348288A1 - Verfahren zur Herstellung einer Zirkoniumoxidschicht - Google Patents

Verfahren zur Herstellung einer Zirkoniumoxidschicht Download PDF

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Publication number
EP0348288A1
EP0348288A1 EP89401714A EP89401714A EP0348288A1 EP 0348288 A1 EP0348288 A1 EP 0348288A1 EP 89401714 A EP89401714 A EP 89401714A EP 89401714 A EP89401714 A EP 89401714A EP 0348288 A1 EP0348288 A1 EP 0348288A1
Authority
EP
European Patent Office
Prior art keywords
acetylacetonate
zirconium
zirconium acetylacetonate
film
coating
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.)
Granted
Application number
EP89401714A
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English (en)
French (fr)
Other versions
EP0348288B1 (de
Inventor
Keiji C/O Nisshin Steel Co. Ltd. Izumi
Takenori C/O Nisshin Steel Co. Ltd. Deguchi
Hidetoshi C/O Nisshin Steel Co. Ltd. Tanaka
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Steel Nisshin Co Ltd
Original Assignee
Nisshin Steel Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Nisshin Steel Co Ltd filed Critical Nisshin Steel Co Ltd
Publication of EP0348288A1 publication Critical patent/EP0348288A1/de
Application granted granted Critical
Publication of EP0348288B1 publication Critical patent/EP0348288B1/de
Expired legal-status Critical Current

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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
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1254—Sol or sol-gel processing
    • 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
    • C23C18/1216—Metal oxides

Definitions

  • This invention relates to a method of preparing a zirconia film, and more particularly to a method of preparing a zirconia film by using a zirconium acetylacetonate suspension formed into a sol (or colloidal solution).
  • Known as methods for preparing zirconia films at low temperatures are (1) a method in which a substrate is coated with a zirconium alkoxide solution comprising zirconium propoxide or zirconium butoxide, followed by hydrolysis and dehydration condensation (Japanese Patent Publication No. 48865/1984, (2) a method in which a substrate is coated with a zirconium octylate solution followed by thermal decomposition (Japanese Unexamined Patent Publication No.
  • the concentration of the zirconium alkoxide may be lowered to retard the rate of hydrolysis in the air, but a lowered concentration makes it necessary to carry out the coating several times to obtain a thick film, thus increasing the coating times.
  • the hydrolysis rate of the zirconium octylate is lower than that of the zirconium alkoxide, and hence no gel is formed even when coated with its alcohol solution having a higher concentration (not less than about 25 g/l). No problems may therefore arise if the alcohol solution prepared is completely used every time the coating is carried out, but, when the solution is not completely used, the remaining solution must be used in a short time before it can be reused.
  • the zirconium octylate has also a large molecular weight of the organic acid group with respect to zirconium, and therefore the yield of zirconia is as low as about 19%.
  • the solution can attain a superior workability and give a thicker film at the first coating than other methods.
  • the acetylacetonate metallic complex is solid, its solubility to organic solvents such as alcohols and aromatic hydrocarbons is not so good that a suspension thereof can only have a concentration of about 0.05 mol/l. For this reason, the film thickness obtained by the first coating is still insufficient, and it has been necessary for obtaining a thick film to use as a solvent a highly viscous solvent such as methyl cellulose or glycol, or increase the coating times.
  • An object of the present invention is to provide a method of preparing a zirconia film with a sufficient thickness by the first coating.
  • Another object of the present invention is to provide a method of preparing a zirconia film by using a coating solution having a superior shelf stability and achievable of a good workability.
  • the method comprises coating a substrate with a zirconium acetylacetonate suspension formed into a sol obtained by carrying out hydrolysis of zirconium acetylacetonate by adding water in an amount of from 10 to 12 mols per mol of zirconium acetylacetonate in an organic solvent solution comprising zirconium acetylacetonate, or an organic solvent solution comprising zirconium acetylacetonate and a different type of acetylacetonate metallic complex added.
  • This method can obtain a thick film at the first coating, and the coating solution used in the method can be stably stored for a long period of time.
  • the zirconium acetylacetonate (CH3COCHCH3)4Zr is a coordinate bond compound, and hence can be formed into a sol by carrying out hydrolysis by adding water, thus making its concentration higher than that in a saturated organic solvent solution. This higher concentration makes it possible to apply the compound in a large quantity than that of a saturated organic solvent solution at the first coating, to provide a thick zirconia film after heating.
  • the theoretical water quantity necessary for completely hydrolyzing the zirconium acetylacetonate is 4 mols per mol of zirconium acetylacetonate, but the water is added in an amount of from 10 to 12 mols.
  • An amount less than 10 mols can not bring about complete dissolution of the zirconium acetylacetonate, resulting in a formation of a suspension, making it impossible to give a thick film at the first coating.
  • An amount more than 12 mols may result in a white and turbid solution in several minutes after hydrolysis to produce precipitates, making it impossible to carry out coating.
  • acetylacetonate metallic complex in addition to the zirconium acetylacetonate for the purpose of improving the properties of the zirconia film, it is also hydrolyzed by water and formed into a sol, and thus a thick film can also be obtained.
  • It includes, for example, titanium acetylacetonate, aluminum acetylacetonate, potassium acetylacetonate, and diethylthallium acetylacetonate, which can be readily hydrolyzed.
  • Thermal decomposition after the coating of the zirconium acetylacetonate (and/or the different type of acetylacetonate metallic complex) formed into the sol may be carried out at 200°C or more in the same manner as conventionaly done.
  • the film may be heated at from 500 to 1,200°C.
  • the resulting zirconia films had a film thickness of 0.25 ⁇ m in the instance where the suspension formed into a sol was used, and 0.05 ⁇ m in the instance where the control suspension was used. These films achieved a strong adhesion, and were free from generation of cracks and uneveness of film thickness.
  • the zirconium acetylacetonate suspension formed into a sol was also allowed to stand for a week in the air (relative humidity: 60 % at 25°C) and thereafter again used, but the same results were obtained as those before it was allowed to stand,
  • zirconia films were formed on SUS304 stainless steel sheets of 0.4 mm thick each in the same procedures as Example 1, to obtain the results that the zirconia films had a film thickness of 0.13 ⁇ m in the instance where the suspension formed into a sol was used, and 0.025 ⁇ m in the instance where the control suspension was used.
  • the stainless steel sheets on which these zirconia films were formed were heated at 800°C for 10 hours, and gains in weight by oxidation was measure to find that they were 0.06 mg/cm2 in the instance where the film was formed using the suspension formed into a sol, and 0.11 mg/cm2 in the instance where the film was formed using the control suspension.
  • SUS304 stainless steel sheets were respectively coated with the resulting suspension formed into a sol and the suspension (control) having been not formed into a sol, following the same procedures as Example 1, followed by heating to thus form an oxide film comprising ZrO2, TiO2 and AIO3 uniformly dispersed.
  • the film formed using the suspension formed into a sol had a thickness of 0.22 ⁇ m.
  • the film formed using the control suspension had a thickness of 0.04 ⁇ m.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Chemically Coating (AREA)
EP19890401714 1988-06-22 1989-06-16 Verfahren zur Herstellung einer Zirkoniumoxidschicht Expired EP0348288B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP63153875A JP2512402B2 (ja) 1988-06-22 1988-06-22 ジルコニア膜の製造方法
JP153875/88 1988-06-22

Publications (2)

Publication Number Publication Date
EP0348288A1 true EP0348288A1 (de) 1989-12-27
EP0348288B1 EP0348288B1 (de) 1992-08-26

Family

ID=15572024

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19890401714 Expired EP0348288B1 (de) 1988-06-22 1989-06-16 Verfahren zur Herstellung einer Zirkoniumoxidschicht

Country Status (3)

Country Link
EP (1) EP0348288B1 (de)
JP (1) JP2512402B2 (de)
DE (1) DE68902597T2 (de)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0358338A2 (de) * 1988-08-12 1990-03-14 Alcan International Limited Verfahren und Zusammensetzung für Oberflächenbehandlung
EP0492826A2 (de) * 1990-12-24 1992-07-01 Dow Corning Corporation Pyrolyseverfahren in umgekehrter Richtung
WO1993005875A1 (fr) * 1991-09-20 1993-04-01 Rhone-Poulenc Chimie Solutions colloidales concentrees de particules monocristalines non agregees d'oxydes de metaux, leur procede de preparation et leur application a l'obtention de films
GB2328876A (en) * 1997-09-04 1999-03-10 Robert Butler Eye medication spray dispenser
EP1084992A1 (de) * 1999-09-13 2001-03-21 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verfahren zur Abscheidung von Zirkonoxid-Schichten unter Verwendung von löslichen Pulvern
WO2003031682A2 (en) * 2001-10-05 2003-04-17 Ekc Technology, Inc. Photolytic conversion process to form patterned amorphous film
US6569547B2 (en) * 2000-10-10 2003-05-27 Matsushita Electric Works, Ltd. Hard tissue repairing materials and the process for producing the same
DE10324910A1 (de) * 2003-05-30 2004-12-23 Vacuumschmelze Gmbh & Co. Kg Metallischer Gegenstand mit elektrisch isolierender Beschichtung sowie Verfahren zur Herstellung einer elektrisch isolierenden Beschichtung
EP3320972A1 (de) * 2016-11-09 2018-05-16 BSH Hausgeräte GmbH Haushaltsgerät mit einer selbstreinigenden, katalytisch aktiven oberfläche und verfahren zum betrieb desselben
WO2018086863A1 (en) * 2016-11-09 2018-05-17 BSH Hausgeräte GmbH Household appliance having a self-cleaning catalytically active surface and a method for operating the same
CN114773051A (zh) * 2022-04-24 2022-07-22 中山大学 一种改良溶胶-凝胶法制备α相的LiZr2(PO4)3固态电解质的方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8980387B2 (en) 2011-10-27 2015-03-17 General Electric Company Method of coating a surface and article incorporating coated surface

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4129434A (en) * 1971-07-08 1978-12-12 Glaverbell Process for forming a metal oxide coating
EP0125507A2 (de) * 1983-04-15 1984-11-21 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Anorganische Zusammensetzung und Verfahren zu ihrer Herstellung

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1210201B (it) * 1985-08-08 1989-09-06 Westinghouse Electric Corp Procedimento per produrre un rivestimento anticorrosivo su un substrato metallico.
JPS6376881A (ja) * 1986-09-19 1988-04-07 Nisshin Steel Co Ltd ジルコニア膜の製造方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4129434A (en) * 1971-07-08 1978-12-12 Glaverbell Process for forming a metal oxide coating
EP0125507A2 (de) * 1983-04-15 1984-11-21 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Anorganische Zusammensetzung und Verfahren zu ihrer Herstellung

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0358338B1 (de) * 1988-08-12 1994-07-27 Alcan International Limited Verfahren und Zusammensetzung für Oberflächenbehandlung
EP0358338A2 (de) * 1988-08-12 1990-03-14 Alcan International Limited Verfahren und Zusammensetzung für Oberflächenbehandlung
EP0492826A2 (de) * 1990-12-24 1992-07-01 Dow Corning Corporation Pyrolyseverfahren in umgekehrter Richtung
EP0492826A3 (en) * 1990-12-24 1993-03-03 Dow Corning Corporation Reverse direction pyrolysis processing
WO1993005875A1 (fr) * 1991-09-20 1993-04-01 Rhone-Poulenc Chimie Solutions colloidales concentrees de particules monocristalines non agregees d'oxydes de metaux, leur procede de preparation et leur application a l'obtention de films
GB2328876B (en) * 1997-09-04 2001-10-24 Robert Butler Eye medication dispenser
GB2328876A (en) * 1997-09-04 1999-03-10 Robert Butler Eye medication spray dispenser
US6860933B2 (en) 1999-09-13 2005-03-01 Fraunhofer-Gesellschaft Zur Forderung Der Angewandten Forschung Process for depositing layers of zirconium oxide using soluble powders
EP1084992A1 (de) * 1999-09-13 2001-03-21 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verfahren zur Abscheidung von Zirkonoxid-Schichten unter Verwendung von löslichen Pulvern
US6569547B2 (en) * 2000-10-10 2003-05-27 Matsushita Electric Works, Ltd. Hard tissue repairing materials and the process for producing the same
WO2003031682A2 (en) * 2001-10-05 2003-04-17 Ekc Technology, Inc. Photolytic conversion process to form patterned amorphous film
WO2003031682A3 (en) * 2001-10-05 2003-08-28 Ekc Technology Inc Photolytic conversion process to form patterned amorphous film
DE10324910A1 (de) * 2003-05-30 2004-12-23 Vacuumschmelze Gmbh & Co. Kg Metallischer Gegenstand mit elektrisch isolierender Beschichtung sowie Verfahren zur Herstellung einer elektrisch isolierenden Beschichtung
DE10324910B4 (de) * 2003-05-30 2005-05-25 Vacuumschmelze Gmbh & Co. Kg Metallisches Halbzeug mit elektrisch isolierender Beschichtung sowie Verfahren zur Herstellung einer elektrisch isolierenden Beschichtung
EP3320972A1 (de) * 2016-11-09 2018-05-16 BSH Hausgeräte GmbH Haushaltsgerät mit einer selbstreinigenden, katalytisch aktiven oberfläche und verfahren zum betrieb desselben
WO2018086863A1 (en) * 2016-11-09 2018-05-17 BSH Hausgeräte GmbH Household appliance having a self-cleaning catalytically active surface and a method for operating the same
CN114773051A (zh) * 2022-04-24 2022-07-22 中山大学 一种改良溶胶-凝胶法制备α相的LiZr2(PO4)3固态电解质的方法

Also Published As

Publication number Publication date
DE68902597T2 (de) 1993-01-21
JP2512402B2 (ja) 1996-07-03
JPH024977A (ja) 1990-01-09
DE68902597D1 (de) 1992-10-01
EP0348288B1 (de) 1992-08-26

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