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EP0677596A1 - Procede de production d'un revetement en ceramique oxydee - Google Patents

Procede de production d'un revetement en ceramique oxydee Download PDF

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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
Application number
EP94929654A
Other languages
German (de)
English (en)
Other versions
EP0677596A4 (fr
Inventor
Taketo Sakuma
Kunichi Miyazawa
Yoshimi Baba
Yoshiki Mizuno
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.)
Advance KK
Original Assignee
Advance KK
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 Advance KK filed Critical Advance KK
Publication of EP0677596A4 publication Critical patent/EP0677596A4/fr
Publication of EP0677596A1 publication Critical patent/EP0677596A1/fr
Ceased legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C18/00Chemical 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
    • C23C18/02Chemical 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
    • C23C18/12Chemical 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
    • C23C18/1204Chemical 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
    • C23C18/1208Oxides, e.g. ceramics
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C18/00Chemical 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
    • C23C18/02Chemical 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
    • C23C18/12Chemical 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
    • C23C18/125Process of deposition of the inorganic material
    • C23C18/1254Sol 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)
EP94929654A 1993-10-14 1994-10-13 Procede de production d'un revetement en ceramique oxydee Ceased EP0677596A1 (fr)

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)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
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

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
No further relevant documents disclosed *
See also references of WO9510640A1 *

Cited By (2)

* Cited by examiner, † Cited by third party
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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