WO2005035818A2 - Diamond coated article and method of its production - Google Patents
Diamond coated article and method of its production Download PDFInfo
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- WO2005035818A2 WO2005035818A2 PCT/US2004/024903 US2004024903W WO2005035818A2 WO 2005035818 A2 WO2005035818 A2 WO 2005035818A2 US 2004024903 W US2004024903 W US 2004024903W WO 2005035818 A2 WO2005035818 A2 WO 2005035818A2
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- layer
- interfacial
- substrate
- carbon
- diamond
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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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
- C23C16/27—Diamond only
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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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/02—Pretreatment of the material to be coated
- C23C16/0272—Deposition of sub-layers, e.g. to promote the adhesion of the main coating
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- 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
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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
- 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
- C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
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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
- 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
- C23C28/325—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with layers graded in composition or in physical properties
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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
- 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
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- 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
- C23C28/341—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 carbide layer
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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
- 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
- C23C28/343—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 DLC or an amorphous carbon based layer, the layer being doped or not
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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
- 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
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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
- 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
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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
- C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
- C23C30/005—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process on hard metal substrates
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
- Y10T428/2495—Thickness [relative or absolute]
- Y10T428/24967—Absolute thicknesses specified
- Y10T428/24975—No layer or component greater than 5 mils thick
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
- Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
- Y10T428/264—Up to 3 mils
- Y10T428/265—1 mil or less
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/30—Self-sustaining carbon mass or layer with impregnant or other layer
Definitions
- the present invention is related to a coated article and, more particularly, to a diamond coated article, consisting of a hard substrate coated with a diamond coating.
- Diamond coating can be deposited on a metallic substrate or on a substrate made out of ceramic composite material.
- metallic substrate may be high-speed steel (HSS) substrate or stainless steel (SS) substrate. Both HSS and SS are alloys of iron (Fe) with carbon (C) and other alloying elements.
- the examples of the substrate made out of composite material may be cemented carbide substrate, which has a structure of tungsten carbide (WC) grains, bound together by a cobalt (Co) binder.
- Diamond coating deposition is carried out at elevated temperatures, usually at 850° C, in the atmosphere of atomic carbon (C) and hydrogen (H).
- C atomic carbon
- H hydrogen
- the amount of shrinkage is governed by the coefficient of thermal extension (CTE).
- CTE's of the diamond coating and the aforementioned substrates differ substantially.
- HSS and SS substrates have CTE of approximately 13 * 10 "6
- cemented carbide substrates have CTE of 3*10 " ⁇ , both large compared with the CTE of diamond of 0.3*10 "6 .
- the substrate shrinks more.
- the diamond coating develops high level of compressive residual stress.
- This CTE mismatch and resulting residual stress buildup limit the thickness of the diamond coating and may result in coating delaminating from the substrate.
- Fe acts as a catalyst converting the adjacent layer of diamond into graphite.
- the detrimental catalytic effect of Fe leads to the formation of the layer of graphitic carbon and degrades the adhesion on diamond-cemented carbide interface.
- Co which is typically used as a binder in cemented carbides, is detrimental to deposition of well-adhered diamond films.
- Co acts as a catalyst converting the adjacent layer of diamond into graphite and degrading the adhesion on diamond- cemented carbide interface.
- the ceramic interfacial layers do not form chemical bonds with diamond and therefore, do not provide good adhesion between the diamond coating and the substrate. As a result, the adhesion between diamond coating and carbon-sensitive substrates remains a problem.
- various techniques, including acid etching have been developed.
- etching of Co binder reduces the interfacial surface strength of the cemented carbide article due to loose WC particles. The loose WC particles provide a weak interface for diamond coating.
- the carbide-forming metal consumes carbon from the surface layers of the cemented carbide, leading to its de-carburization and formation of a brittle ⁇ -phase in case of WC. Also, under the conditions of diamond coating deposition the carbide-forming metal may inter-diffuse into the substrate in case of steel.
- a two-layered protective coating has been proposed, with the first layer consisting of carbon diffusion barrier selected from the group consisting of MetCO, MetCON and MetON atop and adjacent to the substrate and a second (next innermost) wear resistant coating of at least one layer of MetC, MetN or MetCN, where Met is Ti, Hf, V, Zr, Si, B or other metals of subgroup 3-7 of the periodic table of the elements, or a mixture thereof.
- the oxygen containing in the first layer may diffuse away, resulting in changes in the coating properties.
- the proposed design of interfacial layers does not relive stress buildup in diamond coating. Also, the proposed two- layered structure is complicated and expensive to deposit.
- a diamond-coated substrate Disposed between the diamond coating and the substrate is an interfacial composite laminate, comprising at least one ceramic interfacial layer adjacent to and adjoining the substrate and at least one metallic interfacial layer over the ceramic interfacial layer.
- the thickness of the ceramic interfacial layer is greater than the diffusion depth of either atoms from metallic layer or substrate atoms under the conditions of diamond deposition.
- the thickness of the metallic layer is greater than the depth of diffusion of carbon under the conditions of diamond deposition.
- a diamond-coated substrate Disposed between the diamond coating and the substrate is an interfacial composite laminate comprising a ceramic interfacial layer and a metallic interfacial layer.
- an interfacial composite laminate comprising a ceramic interfacial layer and a metallic interfacial layer.
- the top stratum of the metallic layer is converted into carbide due to diffusion of carbon atoms, thus providing good adhesion to diamond coating and a diffusion barrier.
- the outer stratum of the metallic layer is converted into carbide, the inner stratum of the metallic layer is preserved unchanged.
- a diamond- coated steel article having a steel substrate and interfacial composite laminate disposed between the diamond coating and the substrate. At least one interfacial layer of the interfacial composite laminate is metallic and consists of Cr, Ti, Zr, W, Ni or other carbide-forming metals or mixtures thereof.
- the thickness of the metallic interfacial layer is greater than the depth of carbon diffusion under the conditions used during diamond deposition. During deposition of the diamond layer on the metallic layer, the outer stratum of this metallic layer is converted into carbide due to diffusion of carbon atoms, thus providing good adhesion to diamond coating and a diffusion barrier. The thickness of the metallic interfacial layers is greater than the carbon diffusion depth and, thus, the metallic layer is only partially converted into metal carbide. The inner stratum of the metallic layer is preserved unchanged.
- the interfacial composite laminate comprises additional interfacial layers within the aforementioned systems having ceramics, such as nitrides, borides or carbides of transitional metals between the substrate and the metallic interfacial layer, to prevent the inter-diffusion between a metallic interfacial layer and the substrate.
- ceramics such as nitrides, borides or carbides of transitional metals between the substrate and the metallic interfacial layer
- a topcoat of diamondlike carbon such as a mixture of sp2- and sp3-bonded carbon may be provided on top of diamond coating to fill in the roughness valleys between diamond grains.
- the aforementioned articles may be heat-treated after the diamond deposition, resulting in a substrate with a martensite structure.
- a method of producing a steel article coated with diamond coating is provided.
- the steel substrate is first coated with a number of interfacial layers, with at least the top interfacial layer being metal such as Cr, Ti, Ni, W, etc.
- a diamond coating is deposited on top of metallic interfacial layer.
- the outer stratum of the interfacial metallic layer is converted into carbide during the diamond deposition.
- the layer of mixed sp2- and sp3-bonded carbon is deposited by lowering the hydrogen bombardment rate through decrease in flow of hydrogen-producing gas through the chamber.
- a diamond coated cemented carbide article having a cemented carbide substrate and interfacial layers disposed between the diamond coating and the cemented carbide substrate. At least one interfacial layer is metallic. This metallic interfacial layer increases the strength of the cemented carbide article and inhibits the formation of graphite layer during the diamond deposition by reducing the interaction of cobalt within the cemented carbide substrate with the diamond coating.
- a cemented carbide composite material is disclosed.
- the cemented carbide composite has interfacial layers, with at least one interfacial layer selected from a group consisting of high recrystallization temperature amorphous nitrides, high recrystallization temperature amorphous borides, and high recrystallization temperature amorphous carbides.
- Figure 1 represents a cross-sectional view of a composite material according to the teachings of the present invention.
- Figure 1 represents a composite laminate according to the teachings of the present invention.
- the material 10 has a base or substrate layer 12 formed of a carbon sensitive material such as tool steels or ceramic materials.
- a high carbon content layer 16 such as a diamond coated layer.
- an intermediate interfacial barrier laminate 18 Disposed between the diamond coating layer 16 and the substrate layer 12 is an intermediate interfacial barrier laminate 18, which functions to produce a carbide rich layer 20 between the interfacial barrier laminate 18 and the diamond coating layer 16.
- the interfacial layer functions to prevent diffusion of carbon from the diamond coating layer 16 into the substrate layer 12 as well as functions to provide good adhesion between the diamond coating layer 16 and the interfacial barrier laminate 18. While the interfacial barrier laminate 18 is depicted as a single laminate layer, it is envisioned that the interfacial barrier laminate 18 can additionally take the form of a multi-layer laminate structure. [0027] In a multi-layer configuration, at least the top metallic layer 22 of the interfacial barrier laminate 18 consists of Cr, Ti, Zr, W, Ni or other carbide- forming metals or mixtures thereof. During the deposition of diamond, the carbide rich stratum or layer 20 of the interfacial barrier laminate 18 is converted into carbide due to diffusion of carbon atoms.
- the carbide rich stratum 20 of the interfacial barrier laminate layer 18 is formed in the metallic layer 22, which provides good adhesion between the diamond coating layer 16 and the interfacial barrier laminate 18.
- the thickness of the metallic layer 22 is greater than the carbon diffusion depth of the carbide rich stratum 20 and, thus, the metallic layer 22 is only partially converted into carbide.
- the remaining part of the metallic layer 22 has low resistance to plastic deformation at elevated temperatures and is therefore configured to relieve residual stress in the diamond coating layer 16.
- the substrate layer 12 be formed of high speed steel, at least one of the interfacial layers of the interfacial barrier laminate 18 and the substrate layer 12 is a ceramic interfacial layer 24.
- This ceramic interfacial layer 24 is configured to prevent the inter-diffusion of materials between the steel substrate 12 and the metallic interfacial layer 22.
- Additional interfacial layers 26 may be provided consisting of ceramics, such as nitrides, borides or carbides of transitional metals between the steel substrate and a metallic interfacial layer, to further prevent the inter-diffusion of materials between the metallic layer 22 and the substrate layer 12, as well as add stress relieving properties.
- High speed steel is characterized by high strength, hardness and wear resistance.
- the chemical composition of the high speed steel substrate includes 1 % of C, up to 18% of W, up to 10% of Mo, up to 5% of V, and may include other alloying elements.
- Proper heat treatment for this steel includes heating to elevated temperatures with the formation of microstructure of highly alloyed austenite, followed by quenching that leads to a microstructure of martensite.
- the volume of steel increases during this martensite transformation while density decreases.
- Specific volume of austenite with carbon content of 0.2% to 1.4% is 0.12227 to 0.12528 cm 3 /gram, while that of marten cite is in the range of 0.12708 to 0.13061 cm 3 /gram.
- Exposure of high speed steel to high temperature during diamond deposition may change its structure. Namely, the martensite may dissolve and ferrite may form, with a significant drop in hardness and wear resistance.
- Typical chemical composition of stainless steel includes 0.1% of C, 18% of Cr, 10% of Ni, 1% of Ti, and may include other alloying elements.
- similar interfacial layers are disposed between the diamond coating layer 16 and the cemented carbide substrate layer 12.
- At least one layer of the interfacial barrier laminate 18 is a metallic layer 22.
- This metallic layer 22 increases the strength of the cemented carbide article 10 and inhibits the formation of a graphite layer during the diamond deposition by reducing the interaction of cobalt within the cemented carbide substrate with the diamond coating.
- the cemented carbide substrate 12 is a composite material, consisting of carbide grains bound together by a metal matrix.
- the carbides are those of tungsten, WC, titanium, TiC, vanadium, VC, and some others.
- the most widely used metal matrix is cobalt.
- the matrix acts as a tough "glue” or “cement”, holding together hard but brittle tungsten carbide grains ("blocks").
- blocks hard but brittle tungsten carbide grains
- the cemented carbide composite 10 has additional interfacial layers 26, with at least one interfacial layer selected from a group consisting of high recrystallization temperature amorphous nitrides, high recrystallization temperature amorphous borides, and high recrystallization temperature amorphous carbides.
- the diamond coated cemented carbide material 10 has an interfacial layer or layers 26 having a metallic layer 22 which is selected from Cr, Ti, Ni, Zr or W, or other metals or their mixtures, and a ceramic interfacial layer that is selected from the group of borides, nitrides, and carbides of transition metals.
- a metallic layer 22 which is selected from Cr, Ti, Ni, Zr or W, or other metals or their mixtures
- a ceramic interfacial layer that is selected from the group of borides, nitrides, and carbides of transition metals.
- the metallic layer 22 preserves the materials toughness and low resistance to plastic deformation at elevated temperature.
- the metallic layer 22 further deforms plastically after the diamond deposition and reduces the residual stress in diamond coating layer 16. Also it alleviates the weakening effect of the surface imperfections of cemented carbide on its strength.
- the optional additional interfacial layers 26, which serve as a catalyst diffusion barrier, may consist of high recrystallization temperature amorphous nitrides, borides, and carbides.
- a high recrystallization temperature generally corresponds to a temperature higher than the temperature seen by the material during its use.
- the intermediate layer has a thickness of between 2 ⁇ m and 15 ⁇ m and preferably between 5 ⁇ m and 10 ⁇ m.
- the additional interfacial layers 26 can take the form of boride nitrides and carbides of transition materials.
- these carbides can include TiC, TiCN, TiAI, TiN, CrN, CrC, ZrN, and ZrC.
- the additional interfacial layers 26 can take the form of aluminum oxide materials such as Al 2 0 3 .
- an intermediate barrier layer 26 for reducing the formation of graphite can consist of a metallic or semi-metallic layer. This metallic or semi-metallic layer can be formed of material such a Cr, Ti, Zr, or can be silicon.
- the layer of diamond coating layer 16 is deposited over the material. This deposition may be done using, for example, Physical Vapor Deposition. Diamond coating is deposited on top of metallic layer 22, using, for example, Hot Filament Chemical Vapor Deposition.
- a layer 28 of mixed sp2- and sp3-bonded carbon is deposited by lowering the hydrogen bombardment rate through decrease in flow of hydrogen-producing gas through the chamber.
- the article with diamond coating on it may be heat-treated by heating it in vacuum and quenching it in a jet of a noble gas or other nonreactive gas and annealing.
- the mixture of sp2- and sp3-bonded carbon on top of diamond coating functions to fill in the roughness valleys between diamond grains.
- the substrate layer 12 be formed of steel, the entire steel composite may be heat-treated after the diamond deposition, resulting in a substrate layer 12 with a martensite structure. This will further relieve residual stress in the diamond coating layer 16 due to increase in volume of steel substrate layer 12 during martensite transformation.
- a method of producing a steel composite article coated with diamond coating is now described. It is envisioned that the following method is equally applicable to deposition of diamond coatings on other substrate materials.
- the steel substrate is first coated with a number of interfacial layers, with at least the top interfacial layer being metal such as Cr, Ti, Ni, W, etc.
- This deposition may be done using, for example, Physical Vapor Deposition.
- Diamond coating is then deposited on top of metallic interfacial layer, using, for example, Hot Filament Chemical Vapor Deposition.
- the layer of mixed sp2- and sp3-bonded carbon is optionally deposited by lowering the hydrogen bombardment rate through decrease in flow of hydrogen-producing gas through the chamber.
- the article with diamond coating on it may be heat-treated by heating it in vacuum and quenching it in a jet of a noble gas or other nonreactive gas and annealing.
- the interfacial layer 18 can be applied onto the ceramic carbide substrate 12 using CVD, PVD, and electroplating processes or combinations thereof.
- the continuous film will preferably be vapor deposited, sprayed or electrolessly deposited onto the composite using conventional Physical Vapor Deposition (PVD), spraying or electroless a.k.a. autocatalytic) deposition techniques well known in the art.
- PVD Physical Vapor Deposition
- spraying or electroless a.k.a. autocatalytic deposition techniques well known in the art.
- PVD or sputtering can be used to deposit all of the conductive materials identified above as comprising the interface layer.
- the composite is made the cathode in an electroplating cell having an electrolyte containing a salt of the metal being deposited.
- the desired metal deposits out on the surface of the cathodic composite.
- the surface of the composite is seeded with a catalyst and then exposed to a bath containing ions of the metal to be deposited.
- the catalyst initiates reduction of the metal ions to elemental metal, which forms a metal film on the surface of the substrate.
- the material to be plated condenses on the substrate from a vapor thereof.
- the continuous interface film or layer may also comprise a layer of high temperature amorphous carbide material having a higher recrystallization temperature (e.g. > 90%) than the underlying composite substrate.
Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP04779837A EP1677919A2 (en) | 2003-09-29 | 2004-07-30 | Diamond coated article and method of its production |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/673,762 US7195817B2 (en) | 2003-09-29 | 2003-09-29 | Diamond coated article and method of its production |
US10/673,762 | 2003-09-29 |
Publications (2)
Publication Number | Publication Date |
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WO2005035818A2 true WO2005035818A2 (en) | 2005-04-21 |
WO2005035818A3 WO2005035818A3 (en) | 2005-07-21 |
Family
ID=34376687
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2004/024903 WO2005035818A2 (en) | 2003-09-29 | 2004-07-30 | Diamond coated article and method of its production |
Country Status (4)
Country | Link |
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US (1) | US7195817B2 (en) |
EP (1) | EP1677919A2 (en) |
CN (1) | CN1859985A (en) |
WO (1) | WO2005035818A2 (en) |
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US8555921B2 (en) | 2002-12-18 | 2013-10-15 | Vapor Technologies Inc. | Faucet component with coating |
US7866342B2 (en) | 2002-12-18 | 2011-01-11 | Vapor Technologies, Inc. | Valve component for faucet |
US7866343B2 (en) | 2002-12-18 | 2011-01-11 | Masco Corporation Of Indiana | Faucet |
US8220489B2 (en) | 2002-12-18 | 2012-07-17 | Vapor Technologies Inc. | Faucet with wear-resistant valve component |
DE502006005651D1 (en) * | 2005-09-10 | 2010-01-28 | Ixetic Hueckeswagen Gmbh | Wear resistant coating and method of making same |
DE102005054132B4 (en) * | 2005-11-14 | 2020-03-26 | Robert Bosch Gmbh | Valve for controlling a fluid with a tribological system |
CN1986213B (en) * | 2005-12-22 | 2010-12-08 | 鸿富锦精密工业(深圳)有限公司 | Antiwear magnetic coating and its making process |
TWI410507B (en) * | 2005-12-23 | 2013-10-01 | Hon Hai Prec Ind Co Ltd | Magnetic wear resistance film and method for fabricating the same |
CN101395010B (en) * | 2006-03-01 | 2014-01-08 | 通用汽车环球科技运作公司 | Methods for forming articles having apertures and articles having substantially reduced residual compressive stress |
US7833581B2 (en) * | 2006-09-11 | 2010-11-16 | The Hong Kong University Of Science And Technology | Method for making a highly stable diamond film on a substrate |
JP4413958B2 (en) * | 2007-08-31 | 2010-02-10 | ユニオンツール株式会社 | Hard coating for cutting tools |
US20090226715A1 (en) * | 2008-03-04 | 2009-09-10 | Gm Global Technology Operations, Inc. | Coated article and method of making the same |
US8383200B2 (en) * | 2009-05-27 | 2013-02-26 | GM Global Technology Operations LLC | High hardness nanocomposite coatings on cemented carbide |
JP2013532227A (en) * | 2010-04-30 | 2013-08-15 | セメコン アーゲー | Coated object and method for coating an object |
CN101831651B (en) * | 2010-05-25 | 2012-01-04 | 晏双利 | Hard alloy cutter and film plating method of same |
US9487856B2 (en) | 2012-07-22 | 2016-11-08 | Technion Research & Development Foundation Limited | Diamond-coated substrates |
CN105451931B (en) * | 2013-07-22 | 2018-11-23 | 京瓷株式会社 | The manufacturing method of cutting element and the manufacturing method of machined object |
CN103397314B (en) * | 2013-08-15 | 2015-06-17 | 王涛 | Preparation method of diamond coated cutting tool and application of diamond coated cutting tool in preparation of printed circuit board |
WO2015081159A1 (en) * | 2013-11-27 | 2015-06-04 | Uab Research Foundation | Composites comprising nanostructured diamond and metal boride films and methods for producing same |
US10236622B2 (en) * | 2014-07-16 | 2019-03-19 | Siemens Aktiengesellschaft | Subsea electrical connector component |
EP3380645A1 (en) * | 2015-11-27 | 2018-10-03 | CemeCon AG | Coating a body with a layer of diamond and a layer of hard material |
US20180191228A1 (en) * | 2016-12-29 | 2018-07-05 | General Electric | Magnetic apparatus having electrically insulating layer |
CN109750291A (en) * | 2017-11-07 | 2019-05-14 | 深圳先进技术研究院 | A kind of boron-doped diamond electrode and preparation method thereof |
FR3091298B1 (en) * | 2018-12-28 | 2021-01-29 | Commissariat Energie Atomique | Coloring by optical interference of a diamond |
WO2020176928A1 (en) * | 2019-03-01 | 2020-09-10 | Monash University | Graphene coating |
CN111979544B (en) * | 2020-09-22 | 2022-11-15 | 南京航空航天大学 | Method for multi-stage adjustment of tool coating stress by adopting thermotropic phase change film as stress regulation layer |
CN115125479A (en) * | 2022-05-30 | 2022-09-30 | 东莞市华升真空镀膜科技有限公司 | Hard alloy coating cutter and preparation method thereof |
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- 2003-09-29 US US10/673,762 patent/US7195817B2/en not_active Expired - Fee Related
-
2004
- 2004-07-30 WO PCT/US2004/024903 patent/WO2005035818A2/en not_active Application Discontinuation
- 2004-07-30 EP EP04779837A patent/EP1677919A2/en not_active Withdrawn
- 2004-07-30 CN CNA2004800281476A patent/CN1859985A/en active Pending
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US4707384A (en) * | 1984-06-27 | 1987-11-17 | Santrade Limited | Method for making a composite body coated with one or more layers of inorganic materials including CVD diamond |
US4992082A (en) * | 1989-01-12 | 1991-02-12 | Ford Motor Company | Method of toughening diamond coated tools |
US6087025A (en) * | 1994-03-29 | 2000-07-11 | Southwest Research Institute | Application of diamond-like carbon coatings to cutting surfaces of metal cutting tools |
Also Published As
Publication number | Publication date |
---|---|
EP1677919A2 (en) | 2006-07-12 |
US7195817B2 (en) | 2007-03-27 |
US20050069709A1 (en) | 2005-03-31 |
WO2005035818A3 (en) | 2005-07-21 |
CN1859985A (en) | 2006-11-08 |
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