EP0444394A2 - Ceramic spray coating material - Google Patents

Ceramic spray coating material Download PDF

Info

Publication number
EP0444394A2
EP0444394A2 EP91100015A EP91100015A EP0444394A2 EP 0444394 A2 EP0444394 A2 EP 0444394A2 EP 91100015 A EP91100015 A EP 91100015A EP 91100015 A EP91100015 A EP 91100015A EP 0444394 A2 EP0444394 A2 EP 0444394A2
Authority
EP
European Patent Office
Prior art keywords
weight
coating material
spray
ceramic
mold
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.)
Withdrawn
Application number
EP91100015A
Other languages
German (de)
French (fr)
Other versions
EP0444394A3 (en
Inventor
Nobuhiro Sugitani
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.)
Sugitani Kinzoku Kogyo KK
Original Assignee
Sugitani Kinzoku Kogyo 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 Sugitani Kinzoku Kogyo KK filed Critical Sugitani Kinzoku Kogyo KK
Publication of EP0444394A2 publication Critical patent/EP0444394A2/en
Publication of EP0444394A3 publication Critical patent/EP0444394A3/en
Withdrawn legal-status Critical Current

Links

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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
    • C23C4/11—Oxides

Definitions

  • the present invention relates to a ceramic spray coating material comprising zirconia and yttria.
  • porous ceramic layer spray-coated on the inner surface of a mold may be peeled off in long term runs of 30.000 shots or more of casting, and therefore, it has been desired to provide a further increased bonding force to the metal spray-coated layer.
  • the present invention provides a ceramic spray-coating material comprising zirconia and yttria, wherein the purity of a mixture of zirconia and yttria is 99,6% by weight or more.
  • the ceramic spray-coating material according to the present invention has an excellent bonding force, as compared to the prior art material.
  • the composition of the ceramic spray-coating material according to the present invention comprises 98 to 85 % by weight of ZrO2 and 2 to 15 % by weight of Y2O3.
  • the particles of the spray-coating material may be of an average particle size in a range of 20 to 40 ⁇ m, but an average particle size in a range of 10 to 50 ⁇ m is particularly desirable.
  • a ceramic layer formed of such spray-coating material serves to eliminate a gas during casting and in addition thereto, to considerably improve the heat resistance and durability of the mold.
  • the thickness of such layer is in a range of 50 to 500 ⁇ m.
  • the ceramic spray-coating material according to the present invention will now be described as being used, by way of an example, in a convenient production of a discontinuous casting mold of a copper alloy.
  • An Ni-plating layer is formed on an inner surface of the copper alloy mold in an usual manner to a thickness of 50 to 300 ⁇ m, preferably 100 to 200 ⁇ m. If necessary, a powder alloy of Ni/Co/Cr/Y as described in Japanese Patent application No.
  • 89/228343 corresponding to European Patent application 90110605.4-2106, now published as EP-A-0400683, may be applied onto the Ni-plating layer, with cooling with a water-cooling device provided within the mold, to a thickness of 50 to 600 ⁇ m, preferably 200 to 300 ⁇ m by plasma spray-coating at a temperature of about 10.000 to about 5.000 °C or by jet coating at a temperature of about 2.700 °C. Then, a ceramic coating layer of the above-described composition with a high purity (of 99,6 % by weight or more) is applied to a thickness of 50 to 500 ⁇ m, preferably 200 to 300 ⁇ m by a spray coating under a similar condition.
  • a large number of open pores are produced in the ceramic layer and render the ceramic layer porous.
  • the pores providing the porosity are of a size small as they can be observed by a microscope, rather than a size as large as they will cause a ruggedness on a surface of a molded product.
  • the copper alloy mold made in this manner has the porous ceramic layer having open pores which serve to contain a gas generated during casting and to guide the gas outside and hence, any adverse affection due to the gas cannot be exerted to the surface of a molded product. In other words, no blow (ruggedness) is produced.
  • the mold When the ceramic layer is employed in a copper alloy mold, the mold has higher durability and wear resistance, which enables the number of runs of casting corresponding to the number of shots, approximately 30 to 50 % more than the number of runs of 30.000 shots when a lower purity ceramic layer is used, e.g., 40.000 shots or more, without need for applying a soft facing material to the inner surface of the mold.
  • Ni-plating layer having a thickness of 200 ⁇ m is provided, by electro-plating, on an inner surface of a mold made of a copper alloy containing 0,15 % by weight of zirconium and having a coefficient of thermal conductivity of 7. Then, an alloy comprising 57,55 % by weight of Ni, 25 % by weight of Co, 17 % by weight of Cr and 0,45 % by weight of Y is spray-coated at 8.000 °C by a plasma spray-coating process to form a coating film of 150 ⁇ m.
  • a ceramic mixture having a purity of 99,71 % by weight and comprising 91,41 % by weight of ZrO2, 8,3 % by weight of Y2O3, 0,08 % by weight of SiO2, 0,03 % by weight of Fe2O3 and 0,18 % by weight of impurities is applied onto the thus-formed Ni/Co/Cr/Y alloy coating film to a thickness of 250 ⁇ m by a similar spray-coating process.
  • the spray-coating temperature in this spray-coating is of 8.000 °C.
  • a large number of very small pores are present in the ceramic layer, thereby providing a porosity.
  • a permanent mold is made in the same manner as in Example 1, except for use of a ceramic mixture having a purity of 98,93 % and comprising 90,78 % by weight of ZrO2, 8,15 % by weight of Y2O3, 0,38 % by weight of Al2O3, 0,20 % by weight of SiO2, 0,11 % by weight of Fe2O3 and 0,38 % by weight of impurities.
  • the resulting permanent mold had its ceramic layer peeled off a 30.451 runs.

Abstract

A ceramic spray coating material comprising zirconia and yttria, wherein the purity of a mixture of zirconia and yttria is 99,6% by weight or more is described.
This ceramic spray-coating material has an excellent bonding force, as compared to the prior art material.

Description

    Background of the invention Field of the invention
  • The present invention relates to a ceramic spray coating material comprising zirconia and yttria.
    • Description of the prior art
  • There is a continuous casting mold conventional known from Japanese Patent Publication No. 86/005819, which has a Ni-plating layer formed on an inner surface and a Co-Mo-Cr alloy layer spray-coated thereon and comprising of 45 to 65 % by weight of Co, 20 to 40 % by weight of Mo and the balance of Cr. If such continuous casting mold is used as a casting mold for usual discontinuous casting processes, e.g., a low pressure casting or gravity casting process, a disadvantage is encountered: A gas cannot be sufficiently eliminated during casting and hence, a blow (ruggedness) may be produced, resulting in an inferior surface profile of a molded product.
  • For the purpose of overcoming such disadvantage, the applicant has proposed, in Japanese Patent application No. 89/228343, corresponding to European Patent application 90110605.4-2106, now published as EP-A-0400683, a powdered metal spray-coating material which comprises 40 to 60 % by weight of Ni, 20 to 40 % by weight of Co, 15 to 25 % by weight of Cr and 0,1 to 1,0 % by weight of Y, wherein a porous ceramic layer of ZrO₂/Y₂O₃ is provided on the metal spray-coating material.
  • However, the porous ceramic layer spray-coated on the inner surface of a mold may be peeled off in long term runs of 30.000 shots or more of casting, and therefore, it has been desired to provide a further increased bonding force to the metal spray-coated layer.
  • Thereupon, the applicant has made zealous studies for a ceramic spray-coating material with a further increased bonding force and consequently has found that the above disadvantage can be avoided by increasing the purity of a ceramic spray-coating material of ZrO₂/Y₂O₃.
    • Summary of the invention
  • Therefore, the present invention provides a ceramic spray-coating material comprising zirconia and yttria, wherein the purity of a mixture of zirconia and yttria is 99,6% by weight or more.
  • The ceramic spray-coating material according to the present invention has an excellent bonding force, as compared to the prior art material.
    • Detailed description of the invention
  • The composition of the ceramic spray-coating material according to the present invention comprises 98 to 85 % by weight of ZrO₂ and 2 to 15 % by weight of Y₂O₃. The particles of the spray-coating material may be of an average particle size in a range of 20 to 40 µm, but an average particle size in a range of 10 to 50 µm is particularly desirable.
  • When used in a mold, a ceramic layer formed of such spray-coating material serves to eliminate a gas during casting and in addition thereto, to considerably improve the heat resistance and durability of the mold. In general, it is preferable that the thickness of such layer is in a range of 50 to 500 µm.
  • The ceramic spray-coating material according to the present invention will now be described as being used, by way of an example, in a convenient production of a discontinuous casting mold of a copper alloy. An Ni-plating layer is formed on an inner surface of the copper alloy mold in an usual manner to a thickness of 50 to 300 µm, preferably 100 to 200 µm. If necessary, a powder alloy of Ni/Co/Cr/Y as described in Japanese Patent application No. 89/228343, corresponding to European Patent application 90110605.4-2106, now published as EP-A-0400683, may be applied onto the Ni-plating layer, with cooling with a water-cooling device provided within the mold, to a thickness of 50 to 600 µm, preferably 200 to 300 µm by plasma spray-coating at a temperature of about 10.000 to about 5.000 °C or by jet coating at a temperature of about 2.700 °C. Then, a ceramic coating layer of the above-described composition with a high purity (of 99,6 % by weight or more) is applied to a thickness of 50 to 500 µm, preferably 200 to 300 µm by a spray coating under a similar condition. A large number of open pores are produced in the ceramic layer and render the ceramic layer porous. The pores providing the porosity are of a size small as they can be observed by a microscope, rather than a size as large as they will cause a ruggedness on a surface of a molded product.
  • The copper alloy mold made in this manner has the porous ceramic layer having open pores which serve to contain a gas generated during casting and to guide the gas outside and hence, any adverse affection due to the gas cannot be exerted to the surface of a molded product. In other words, no blow (ruggedness) is produced.
  • When the ceramic layer is employed in a copper alloy mold, the mold has higher durability and wear resistance, which enables the number of runs of casting corresponding to the number of shots, approximately 30 to 50 % more than the number of runs of 30.000 shots when a lower purity ceramic layer is used, e.g., 40.000 shots or more, without need for applying a soft facing material to the inner surface of the mold.
  • The present invention will now be described in more detail by way of Example and Comparative Example.
    • Example
  • An Ni-plating layer having a thickness of 200 µm is provided, by electro-plating, on an inner surface of a mold made of a copper alloy containing 0,15 % by weight of zirconium and having a coefficient of thermal conductivity of 7. Then, an alloy comprising 57,55 % by weight of Ni, 25 % by weight of Co, 17 % by weight of Cr and 0,45 % by weight of Y is spray-coated at 8.000 °C by a plasma spray-coating process to form a coating film of 150 µm.
  • A ceramic mixture having a purity of 99,71 % by weight and comprising 91,41 % by weight of ZrO₂, 8,3 % by weight of Y₂O₃, 0,08 % by weight of SiO₂, 0,03 % by weight of Fe₂O₃ and 0,18 % by weight of impurities is applied onto the thus-formed Ni/Co/Cr/Y alloy coating film to a thickness of 250 µm by a similar spray-coating process. The spray-coating temperature in this spray-coating is of 8.000 °C. A large number of very small pores are present in the ceramic layer, thereby providing a porosity.
  • When the permanent mold made in this manner was used in casting of a magnesium alloy casing for an automobile engine while being cooled to a temperature of 350 to 400 °C, and even if 40.000 shots were conducted, any change on the surface of the mold was still not observed and the surface profile of a molded product was good.
    • Comparative Example
  • A permanent mold is made in the same manner as in Example 1, except for use of a ceramic mixture having a purity of 98,93 % and comprising 90,78 % by weight of ZrO₂, 8,15 % by weight of Y₂O₃, 0,38 % by weight of Al₂O₃, 0,20 % by weight of SiO₂, 0,11 % by weight of Fe₂O₃ and 0,38 % by weight of impurities. The resulting permanent mold had its ceramic layer peeled off a 30.451 runs.

Claims (1)

  1. A ceramic spray coating material comprising zirconia and yttria, wherein the purity of a mixture of zirconia and yttria is 99,6% by weight or more.
EP19910100015 1990-01-29 1991-01-02 Ceramic spray coating material Withdrawn EP0444394A3 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP16153/90 1990-01-29
JP2016153A JPH03223455A (en) 1990-01-29 1990-01-29 Ceramic thermal spraying material

Publications (2)

Publication Number Publication Date
EP0444394A2 true EP0444394A2 (en) 1991-09-04
EP0444394A3 EP0444394A3 (en) 1991-10-02

Family

ID=11908562

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19910100015 Withdrawn EP0444394A3 (en) 1990-01-29 1991-01-02 Ceramic spray coating material

Country Status (3)

Country Link
EP (1) EP0444394A3 (en)
JP (1) JPH03223455A (en)
CA (1) CA2035160A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL1007830C2 (en) * 1997-12-18 1999-06-21 Hoogovens Staal Bv Mold for continuous casting of metal and method for continuous casting therewith.
WO2000056481A1 (en) * 1999-03-23 2000-09-28 Cast Centre Pty. Ltd. Die coatings for gravity and low pressure die casting
EP1163065B1 (en) * 1999-02-03 2005-02-16 Outokumpu Oyj Casting mould for manufacturing a cooling element

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05132752A (en) * 1991-06-13 1993-05-28 T-P Kogyo Kk Method for thermally spraying ceramic on casting mold
US7955708B2 (en) * 2005-10-07 2011-06-07 Sulzer Metco (Us), Inc. Optimized high temperature thermal barrier
US8603930B2 (en) 2005-10-07 2013-12-10 Sulzer Metco (Us), Inc. High-purity fused and crushed zirconia alloy powder and method of producing same
US7799716B2 (en) * 2006-03-03 2010-09-21 Sulzer Metco (Us), Inc. Partially-alloyed zirconia powder
JP5765567B2 (en) * 2010-08-05 2015-08-19 アイシン精機株式会社 Die casting mold parts
JP6266093B2 (en) * 2014-04-07 2018-01-24 三菱電機株式会社 Heat exchanger and air conditioner
CN112759950B (en) * 2020-10-28 2022-03-11 北京理工大学 YSZ/graphene composite sealing coating and preparation method thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4485151A (en) * 1982-05-06 1984-11-27 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Thermal barrier coating system

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5887273A (en) * 1981-11-18 1983-05-25 Hitachi Ltd Parts having ceramic coated layer and their production
JPS5895678A (en) * 1981-12-01 1983-06-07 工業技術院長 Heat resistant ceramic coating method
JPH0715141B2 (en) * 1982-11-26 1995-02-22 株式会社東芝 Heat resistant parts
JPS61250161A (en) * 1985-04-30 1986-11-07 Riken Corp Cylinder liner

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4485151A (en) * 1982-05-06 1984-11-27 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Thermal barrier coating system

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
THIN SOLID FILMS, vol. 119, no. 2, September 1984, pages 159-171, Lausanne, CH; N.R. SHANKAR et al.: "Neutron and X-ray diffraction of plasma-sprayed zirconia-yttria thermal barrier coatings" *
THIN SOLID FILMS, vol. 150, no. 1, 22nd June 1987, pages 15-40, Lausanne, CH; S. STECURA: "New ZrO2-Yb2O3 plasma-sprayed coatings for thermal barrier applications" *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL1007830C2 (en) * 1997-12-18 1999-06-21 Hoogovens Staal Bv Mold for continuous casting of metal and method for continuous casting therewith.
EP0924011A1 (en) * 1997-12-18 1999-06-23 Hoogovens Staal B.V. Casting mould for the continuous casting of metal, and method for continuous casting using this casting mould
EP1163065B1 (en) * 1999-02-03 2005-02-16 Outokumpu Oyj Casting mould for manufacturing a cooling element
WO2000056481A1 (en) * 1999-03-23 2000-09-28 Cast Centre Pty. Ltd. Die coatings for gravity and low pressure die casting

Also Published As

Publication number Publication date
EP0444394A3 (en) 1991-10-02
JPH03223455A (en) 1991-10-02
CA2035160A1 (en) 1991-07-30

Similar Documents

Publication Publication Date Title
CA1095342A (en) Duplex coating for thermal and corrosion protection
US4594106A (en) Spraying materials containing ceramic needle fiber and composite materials spray-coated with such spraying materials
EP0444394A2 (en) Ceramic spray coating material
US6238807B1 (en) Thermal spraying composite material containing molybdenum boride and a coat formed by thermal spraying
JPS648072B2 (en)
US6045928A (en) Thermal barrier coating system having a top coat with a graded interface
US4678720A (en) Silver-copper-titanium brazing alloy
US5143541A (en) Process for producing powdered metal spray coating material
JPH0515781B2 (en)
EP0480727A1 (en) Coated hearth roll and process for its production
US5194339A (en) Discontinuous casting mold
KR20000039445A (en) Ceramic complex powdered material for amorphous thermal spraying coating
EP0440013A2 (en) Water-dispersible, heat-resistant composition and uses thereof
JPH0465143B2 (en)
JPH0517305B2 (en)
JP2573350B2 (en) Permanent mold for cast products made of aluminum alloy or magnesium alloy
US5411804A (en) Water-dispersible, heat-resistant composition and use thereof
JP2536320B2 (en) Copper alloy casting mold
JPS6264449A (en) Coating method for metallic mold for casting low melting metal
JP3013461B2 (en) Continuous casting mold
JPH04103750A (en) Formation of wear resistant coating layer
JP3245338B2 (en) Hot chamber die casting machine for low aluminum zinc base alloy
JPH0517304B2 (en)
JPH0659516B2 (en) Functionally gradient layer provided on metal product and method for providing the functionally graded layer
JPH02155532A (en) Permanent metallic mold made of cu alloy for casting

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): CH DE FR GB IT LI

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): CH DE FR GB IT LI

17P Request for examination filed

Effective date: 19920309

17Q First examination report despatched

Effective date: 19920722

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN

18W Application withdrawn

Withdrawal date: 19921121