EP1612295A1 - Substrat de métal enduit et procédé pour sa préparation - Google Patents

Substrat de métal enduit et procédé pour sa préparation Download PDF

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Publication number
EP1612295A1
EP1612295A1 EP05012216A EP05012216A EP1612295A1 EP 1612295 A1 EP1612295 A1 EP 1612295A1 EP 05012216 A EP05012216 A EP 05012216A EP 05012216 A EP05012216 A EP 05012216A EP 1612295 A1 EP1612295 A1 EP 1612295A1
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EP
European Patent Office
Prior art keywords
layer
metal substrate
coated metal
wear protection
protection layer
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Withdrawn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
EP05012216A
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German (de)
English (en)
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.)
Fachhochschule Schmalkalden
Original Assignee
Fachhochschule Schmalkalden
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Filing date
Publication date
Application filed by Fachhochschule Schmalkalden filed Critical Fachhochschule Schmalkalden
Publication of EP1612295A1 publication Critical patent/EP1612295A1/fr
Withdrawn legal-status Critical Current

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    • 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
    • C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
    • C23C10/18—Solid state diffusion of only metal elements or silicon into metallic material surfaces using liquids, e.g. salt baths, liquid suspensions
    • 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
    • C23C18/1229—Composition of the substrate
    • C23C18/1241—Metallic substrates
    • 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
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1283—Control of temperature, e.g. gradual temperature increase, modulation of temperature
    • 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
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/347—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with layers adapted for cutting tools or wear applications
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/36—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including layers graded in composition or physical properties

Definitions

  • the invention relates to a coated metal substrate with a wear protection layer, which has residual compressive stresses and a process for its preparation.
  • Hard material layers are applied to reduce wear, especially in tools to increase the service life.
  • the functional layers are often subject to tensile stresses due to different coefficients of thermal expansion of the wear protection layer material and the substrate material. As the tensile stresses increase, the intended increase in wear resistance decreases. Often too high tensile stresses even lead to the detachment of the layers from the substrate. This also applies to the material combination carbide substrate / oxide ceramic layer, in particular Al 2 O 3 layer.
  • the hard material layers are applied to the substrate by classical methods of PVD (physical vapor deposition) or CVD (chemical vapor deposition). It is disadvantageous that tensile stresses occur in particular in the combination of cemented carbide substrate / Al 2 O 3 layer.
  • a coated cutting tool with high abrasion resistance for the high-speed cutting of steel, which has a hard sintered substrate and a hard coating, which is applied to the surface of the substrate.
  • the hard coating has a layer of hard material as an inner layer having an average thickness between 0.1 .mu.m and 10 .mu.m and a remanent compressive stress applied by physical evaporation, and an aluminum oxide layer as outer layer having a thickness of between 0.1 .mu.m and 5 .mu.m, which is formed by chemical Evaporation is applied at medium temperatures.
  • DE 34 43 329 A1 discloses a method for producing corrosion-resistant wear protection layers with chromium end layer specified, consisting of a 5 to 30 microns thick nickel intermediate layer and a 10 to 40 microns thick chromium end layer, wherein the nickel intermediate layer is applied to the carrier material in that it is under a compressive residual stress of 20 to 60 MPa and then the final chromium layer is applied in a known manner.
  • the compressive stresses are generated in these two methods, however, in an intermediate layer and not in the actual functional layer, namely the wear protection layer.
  • DE 101 23 554 A1 describes the generation of compressive stresses by subsequent blasting.
  • This method serves to increase the compressive residual stress or to lower the inherent tensile stress of an outer or an outermost, by CVD, PCVD or PVD on a hard metal, cermet or ceramic substrate body applied hard material layer, wherein the coated substrate body after the coating of a dry jet treatment using a granular blasting medium is subjected.
  • the blasting agent in this case has a maximum diameter of 150 .mu.m, preferably of at most 100 .mu.m.
  • the hard material layers to reduce wear, thereby increasing the service life of tools in particular, are applied to the substrate by conventional PVD (physical vapor deposition) or CVD (chemical vapor deposition) methods.
  • the invention has for its object to provide a coated metal substrate and a method for its production, in which the compressive stresses and a high adhesive strength.
  • the object is achieved with a substrate having the features specified in claim 1 and with a method having the features specified in claim 14.
  • the process according to the invention uses wet-chemical process steps, for example the sol-gel technology, for the production of oxide-ceramic hard coatings.
  • Hard material layers are preferably produced from Al 2 O 3 .
  • a precursor of the oxide in the form of sol or gel is applied to the substrate.
  • the sol or the gel is converted by a two-stage firing process into the desired hard material modification.
  • the layer has good adhesion when either the substrate or an additionally applied intermediate layer has suitable elements which diffuse into the wear layer. At the same time, these elements cause the generation of residual compressive stresses in the functional layer.
  • the absolute level of the voltages can be selected up to a certain range. Subsequent treatment of the layer is not necessary. Also, it is not necessary to apply an intermediate layer with compressive residual stresses.
  • the example describes a metal substrate 1 made of hard metal, which is provided with a layer material made of Al 2 O 3 .
  • This layered substance is characterized by high hardness and by a relatively low thermal conductivity compared to coating materials with a high metallic bond fraction. These properties are very beneficial for coatings designed for high speed machining.
  • the deposition of such substances by conventional coating methods, for example by CVD or PVD method, is complicated.
  • a solid carbide tool is used as the metal substrate 1, a solid carbide tool is used as the metal substrate 1, a solid carbide tool is used as the metal substrate 1, a solid carbide tool is used as the metal substrate 1, a solid carbide tool is used.
  • the layer thickness should be, for example, in the range of 0.5 to 2.0 microns.
  • the liquid sol the starting substance
  • the process of hydrolysis produces a gel that is converted into an oxide ceramic by a subsequent multi-stage heat treatment.
  • the starting material for producing a layer can also be redispersed by a product produced by the sol-gel process.
  • the starting product Disperal P2 has proved to be advantageous for coating.
  • 1.75 g of disperal are redispersed in 10 ml of water for a single layer thickness in the range between 0.5 and 2.0 microns.
  • To produce an oxide ceramic layer it is necessary to wet the metal substrate 1 with the liquid sol. This process can be carried out with all known methods for coating from the liquid state. For spraying complex shapes, the spray-coating process is advantageous.
  • the cemented carbide substrate 1 does not have elements with which compressive stresses can be set, the hardmetal surfaces are coated with an additional intermediate layer of titanium before the coating with the sol.
  • a PVD coating was performed.
  • the thickness of the intermediate layer should not be more than 0.1 microns.
  • the titanium is distributed in a gradient-like manner from the interface at which the intermediate layer 4 and wear protection layer 2 touch, into the wear protection layer 2 and forms an elemental gradient 3.
  • a thermal treatment follows. For this purpose, drying at 100 ° C, calcining at 500 ° C and the burning of the coating substance at 1000 ° C for adjusting a layer of a ⁇ -phase, which contains portions of the corundum phase. At the same time, the firing process brings about the connection to the metal substrate 1.
  • the boundary conditions of the overall process can be used to influence the properties of the wear protection layer 2 and the composite formed from the wear protection layer 2 and the metal substrate 1.
  • the selection of the elements of the intermediate layer 4 and the thermal treatment during the production of the layer already set the compressive stress state in the wear protection layer 2 via an athermal stress component. Subsequent treatment, such as blasting the surface, is not required.
  • the corundum layer ( ⁇ -Al 2 O 3 ) is the modification of the highest hardness Al 2 O 3 .
  • corundum also has a tremendous brittleness.
  • a gradient of ⁇ - / ⁇ -Al 2 O 3 in the wear-resistant layer 2 can advantageously be set.
  • the service life of these layers increases significantly over layers with a pure corundum phase. This phase gradient can also be influenced by the layer thickness or by the number of individual coatings in the case of multiple layers.
  • the ceramic layers are mostly nanocrystalline and have no fiber textures.
  • the adhesive strength of these layers is high.
  • the layers are reproducible safely produced. Because of the high purity of the starting materials, the layers have the same properties in all layers.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
EP05012216A 2004-06-07 2005-06-07 Substrat de métal enduit et procédé pour sa préparation Withdrawn EP1612295A1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE102004027718 2004-06-07

Publications (1)

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EP1612295A1 true EP1612295A1 (fr) 2006-01-04

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0188369A2 (fr) * 1985-01-14 1986-07-23 Raychem Limited Article à enduction réfractaire
JPH04232248A (ja) * 1990-12-28 1992-08-20 Toyota Central Res & Dev Lab Inc 多層絶縁性構造体およびその製造方法
US6077344A (en) * 1997-09-02 2000-06-20 Lockheed Martin Energy Research Corporation Sol-gel deposition of buffer layers on biaxially textured metal substances

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0188369A2 (fr) * 1985-01-14 1986-07-23 Raychem Limited Article à enduction réfractaire
JPH04232248A (ja) * 1990-12-28 1992-08-20 Toyota Central Res & Dev Lab Inc 多層絶縁性構造体およびその製造方法
US6235402B1 (en) * 1995-04-10 2001-05-22 Ut-Battelle, Llc Buffer layers on biaxially textured metal substrates
US6077344A (en) * 1997-09-02 2000-06-20 Lockheed Martin Energy Research Corporation Sol-gel deposition of buffer layers on biaxially textured metal substances

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 016, no. 581 (C - 1012) 21 December 1992 (1992-12-21) *

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