US3837896A - Sintered cemented carbide body coated with two layers - Google Patents

Sintered cemented carbide body coated with two layers Download PDF

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Publication number
US3837896A
US3837896A US00303362A US30336272A US3837896A US 3837896 A US3837896 A US 3837896A US 00303362 A US00303362 A US 00303362A US 30336272 A US30336272 A US 30336272A US 3837896 A US3837896 A US 3837896A
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layer
layers
coating
substratum
hard metal
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J Lindstrom
B Jonsson
F Ohlsson
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Santrade Ltd
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Sandvik AB
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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
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/32—Carbides
    • 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
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/32—Carbides
    • C23C16/325—Silicon carbide
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/34—Nitrides
    • 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
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/34—Nitrides
    • C23C16/342—Boron nitride
    • 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
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/34—Nitrides
    • C23C16/345—Silicon nitride
    • 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
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/36—Carbonitrides
    • 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
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/403—Oxides of aluminium, magnesium or beryllium
    • 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
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/405—Oxides of refractory metals or yttrium
    • 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
    • C23C16/44—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 method of coating
    • C23C16/448—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 method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
    • C23C16/4488—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 method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials by in situ generation of reactive gas by chemical or electrochemical reaction
    • 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
    • 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
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/922—Static electricity metal bleed-off metallic stock
    • Y10S428/923—Physical dimension
    • Y10S428/924—Composite
    • Y10S428/926—Thickness of individual layer specified
    • 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
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/922—Static electricity metal bleed-off metallic stock
    • Y10S428/9335—Product by special process
    • Y10S428/938—Vapor deposition or gas diffusion
    • 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
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12014—All metal or with adjacent metals having metal particles
    • Y10T428/12028—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, etc.]
    • Y10T428/12049—Nonmetal component
    • Y10T428/12056—Entirely inorganic
    • 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
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    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12014—All metal or with adjacent metals having metal particles
    • Y10T428/12028—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, etc.]
    • Y10T428/12063—Nonparticulate metal component
    • Y10T428/12069—Plural nonparticulate metal components
    • Y10T428/12076—Next to each other
    • 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
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    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12014—All metal or with adjacent metals having metal particles
    • Y10T428/12028—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, etc.]
    • Y10T428/12063—Nonparticulate metal component
    • Y10T428/12104—Particles discontinuous
    • Y10T428/12111—Separated by nonmetal matrix or binder [e.g., welding electrode, etc.]
    • 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
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    • 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

Definitions

  • hard metal e.g., cutting inserts
  • wear-resistant, extremely thin, ceramic layers which, in certain cases, have caused improved wear resistance, and in the case of cutting inserts particularly good cutting results and increased tool life were noted.
  • the ceramic surface layer has principally consisted of A1 and/or ZrO
  • the product may be regarded as a combination in which the known great wear resistance of ceramic inserts as well as the relatively good toughness of cemented carbide have been exploited.
  • the coating layer has been produced by deposition from a gaseous phase. This method has meant extremely uniform and thin layers which has not been reached in earlier-used methods, as for instance enameling of hard metal.
  • the coated hard metal body is thus characterized in that the thin surface coating consists of two successive layers containing no binder material.
  • the outer layer consists of one or more extremely wear-resistant layers of aluminum oxide and/or zirconium oxide
  • the intermediate layer situated next to the cutting body, consists of one or more layers of one or more carbides and/or nitrides of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, silicon and/or boron, i.e. except silicon and boron, metals in the 4th 6th subgroups of the periodic system.
  • the thickness of the abovedescribed intermediate layer, and also of the surface layer may be varied in certain limits whilst still maintaining the favorable properties.
  • thinner carbide or nitride layers may be used than in known merely carbide-coated hard metal inserts, in which have been found optimum properties for example at 4 gm thick TiC layers.
  • the thickness shall be at the least 0.5 pm.
  • Optimum results have been found when the thickness of the inner layer has been 1-10 pm and preferably 2-6 am.
  • the thickness of the outer, ceramic, layer should be 02-20 pm, preferably 0.55 pm. We have thus found that even very thin oxide layers, applied upon barrier layers of nitride and/or oxide, cause a considerable improvement in the wear resistance, at maintained toughness.
  • the binder metal e.g., Co
  • the binder metal seems to have a considerable influence on the rate of the coating operation on the formation of whiskers and the adherence of the layer to the substrate.
  • the binder metal has probably an accelerating effect on the growth of the oxide layer, which will preferably be nucleated on the binder phase surfaces of the hard metal. Carbon also causes a similar behavior.
  • the coating be uniform and finegrained, and also that the layer have good adherence.
  • the speed of the coating process must be slow, which now has been made possible according to the invention by impeding the influence of the binder metal and carbon, i.e., eliminating their accelerating effect on the growth of the layer. Too high rate of formation of the layer means large grains and whiskers, which give porous layers and bad adherence.
  • the surface of the substratum must be well-defined, uniform and homogeneous, so that the growth of the layer can be initiated at as many close points on the surface as possible. From the following it is realized that the surface of the hard metal substratum does not fulfill this demand. The adherence is thus acceptable only between the layer and the binder metal grains of the substratum, while it is less good between the layer and the carbide grains of the substratum.
  • Binder metals e.g., Co
  • Binder metals may also diffuse through the formed oxide layer at the temperature of the deposition.
  • the diffusion rate of Co is thus very low in a layer of carbide and/or nitride.
  • Another advantage of using an intermediate layer according to the invention is a favorable gradual transition between the extremely wear-resistant surface layer and the relatively tough substratum.
  • Carbideor nitride layers. as of TiC or TiN, have namely toughness and wear-resistance properties placing them between aluminum oxide (ceramic cutting inserts) and cemented carbide.
  • AlCl AlBr or AIF
  • CO H O
  • the intermediate layer prevents carburization of the hard metal substratum, which would lead to bad toughness.
  • the intermediate layer of carbide and- /or nitride has a favorable influence as a barrier to carbon diffusion from the substratum.
  • the binder metal phase of cemented carbides is always surface oxidized in air, and becomes it soon in the atmosphere of depositing oxide layers, even if the hard metal surface has been pre-reduced. Therefore. it is expected that this oxide (II state) would form stable spinel bindings with A1 (III state). Also bonds between IV-state oxides as ZrO and II-stage oxides as CoO are usually strong. It is therefore surprising that a stronger bond is obtained between for example TiC on the one hand and A1 0 or respectively ZrO on the other hand. The effect is probably connected with the slower depo sition rate in the presence of the TiC layer.
  • the coating process is done in at least two separate steps and in separate facilities.
  • the first step or partial process consists of forming a barrier layer, i.e., carbide and/or nitride layer, and the second step or partial process consists of possible oxidizing the surface of the barrier and formation of a surface layer of Al O the oxidation step possibly being done as a separate step in a separate apparatus; or
  • the whole coating process i.e., the formation of a barrier layer, the possible oxidizing of the surface ofthe substratum or the barrier and the coating of the barrier with a surface layer of AI O is done in one and the 5 same operation by conducting gaseous reagents by turn and gradually adapting the temperature and pressure conditions in the coating reactor.
  • oxide layers as for example first Al O and then ZrO can be applied upon mixed layers on successive layers of carbide and nitride.
  • the barrier layers may also be applied to alternative methods as for example sputtering.
  • FIG. 1 is a principle sketch of production apparatus useful in carrying out the invention.
  • FIG. 2 is a principle sketch of alternative detail in the apparatus according to FIG. 1.
  • the apparatus shown in FIG. 1 consists of gas sources, for example gas tubes 1, 2 for supplying hydrogen respectively methane and/or nitrogen.
  • Conduits 3 and 4 from respective source units unite into a conduit 5, through which the gas mixture is brought to a vessel 6 in which a metal halide, for example TiCl, is heated to evaporation, after which the composite gas is conducted to a reactor 11 via a joint conduit 9.
  • the gas mixture passes a heat exchanger 7 controlled by a thermostat 8 for adjusting the content of TiC], in the gas.
  • reactor 11 which is heated by a furnace 10, the substratum is placed for coating.
  • From the reactor vessel 11 the gas is sucked out via a valved conduit 12 and a cooling trap 13. Evacuation of gas from the system is effected via a conduit 14 by the help of a vacuum pump 15 having an outlet conduit 16.
  • the apparatus sketched in FIG. 2 shows the use of a chlorination reactor 25 for chlorination of Al respectively Zr, for example in the form of grains or chips 26.
  • a chlorination reactor 25 for chlorination of Al respectively Zr, for example in the form of grains or chips 26.
  • hydrogen from a gas source 1 is mixed via conduits 19, with chlorine, alternatively hydrochloric acid gas, from a chlorine gas alternatively hydrochloric acid source 17, and the mixture is brought to chlorination reactor via a conduit 21.
  • the gas mixture from chlorination reactor 25 is then mixed with hydrogen and carbon monoxide (not necessary) and carbon dioxide from gas sources 18 respectively 28.
  • the resulting mixture is brought to coating reactor 11 via valved conduit 27.
  • Example 1 sisted of a mixture containing TiCh, 8% CH and 82% H manufactured in a normal way, was brought to the reactor in one single conduit.
  • the pressure in the reactor was maintained at torr (mm Hg) by sucking out the gas from the reaction vessel by means of a vacuum pump protected from corrosive reaction products (for instance l-lCl) by the help of a cooling trap with liquid nitrogen situated ahead of the pump. In this way a linear gas flow rate of l m/sec was obtained in the charge.
  • the treatment went on for 2 hours.
  • the 3,000 inserts were treated in an apparatus nearly identical to the one described, the gas supply system being modified, however, so that a gas with the composition 70% H 5% CO CO and 5% AlCl could be dosed.
  • the temperature of the substratum was l,l00 C. and the pressure 15 torr.
  • a linear gas flow rate of 3 m/sec was used.
  • the binding between the A1 0 layer and TiC layer was good and no embrittling n-phase had been formed in the boundary layer, cemented carbide-TiC.
  • Example 2 Also barrier layers of TiN have been manufactured in a way analogous to Example 1.
  • the gas composition was changed, however, to 10% TiCl 30% N and 60% H
  • As a result of the treatment a fine-grained, tight, layer of about 3 um was obtained (essentially TiN but with some amount of TiC because of a slight carbon diffusion from the substratum).
  • the amount of embrittling *q-phase because of decarburizing was very small, however.
  • a second step the 3,000 inserts were treated in an apparatus identical to the pre-treating equipment, the gas supply system being modified, however, so that a gas composed of 70% H 5% CO 20% CO and 5% ZrCl could be dosed at l,000C.
  • the pressure was 15 torr and the linear gas flow rate 5 m/sec.
  • Example 3 Having the same process conditions as in Example 1, the whole coating was done in one apparatus without intermediate cooling of the inserts. Double gas supply systems were used, one for TiCl (connected during the first period of the coating) and the other for AlCl Between the two coating periods there was used only one vacuum pumping with a view to change gas atmosphere. (A gradual transition, i.e., an intermediate simultaneous deposition is also possible. The simultaneous deposition may possibly go on all the second coating period. Also titanium oxide, possibly dissolved in TiC, will then be obtained in the M 0 layer). The result corresponded to the result of Example 1.
  • Example 4 The process was performed in accordance with Example 3 with the exception that an oxidation step was interposed between the two periods. After a first vacuum pumping in order to remove TiCL, and CH an oxidizing gas was introduced, for example hydrogen saturated with water vapor at 30C. After renewed vacuum pumping the aluminum oxide was deposited.
  • Example 5 The deposition process for A1 0 was done as in Example l but upon hard metal inserts coated with a 2 pm thick layer of TiC on one or more faces by means of sputtering.
  • Example 6 there are results from cutting tests, in which cutting inserts according to the invention have been compared with earlier known inserts.
  • Example 6 The cutting test was done in the form of turning on a workpiece of a carbon steel having a C content of l% and a hardness of about HB 300, under the following cutting conditions:
  • the hard metal grade according to ISO P30 had the composition (in by weight): 9.5% Co, 12% TiC, 6% TaC, 4% NbC and the balance being WC.
  • Example 7 Coating of 3,000 sintered hard metal cutting inserts was performed in a similar manner as described in Example 1 except some differences mentioned in the following.
  • the hard metal grade consisted of 75% WC, 9.5% Co and 15.5% (all 7( by volume) cubic carbides in the form of TiC, TaC and NbC.
  • the first treatment involving coating with a barrier layer of TiC, went on for 8 hours and resulted in a layer of about am thickness.
  • the pressure was 10 torr and a linear gas flow rate of 4 m/sec was used. After a coating time of 5 hours, a well adherent layer of A1 0 with a thickness of 0.8 nm had been formed.
  • Compound body consisting of a core or substratum of sintered cemented carbide containing a small quantity of a binder metal, on which core or substratum is a very thin and extremely uniform surface coating with higher wear resistance than that of the core or substratum, in which said thin coating consists of two layers applied one above the other by chemical vapor deposition, neither of the layers containing binder metal, the outer layer having a thickness of 02-20 am and consisting of at least one extremely wear resistant deposit consisting essentially of ceramic material selected from the group consisting of aluminum oxide and zirconium oxide and the inner layer lying next to the core or substratum having a thickness of 1-10 am and consisting of at least one coat of at least one member selected from the group consisting of the carbides and nitrides of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Si and B.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Electrochemistry (AREA)
  • Chemical Vapour Deposition (AREA)
  • Laminated Bodies (AREA)
  • Polishing Bodies And Polishing Tools (AREA)
  • Cutting Tools, Boring Holders, And Turrets (AREA)
  • Physical Vapour Deposition (AREA)
US00303362A 1971-11-12 1972-11-03 Sintered cemented carbide body coated with two layers Expired - Lifetime US3837896A (en)

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JP (1) JPS5213201B2 (enrdf_load_stackoverflow)
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CA (1) CA972233A (enrdf_load_stackoverflow)
DE (1) DE2253745C3 (enrdf_load_stackoverflow)
ES (1) ES408523A1 (enrdf_load_stackoverflow)
FR (1) FR2170383A5 (enrdf_load_stackoverflow)
GB (1) GB1394108A (enrdf_load_stackoverflow)
IT (1) IT969848B (enrdf_load_stackoverflow)
PL (1) PL79682B1 (enrdf_load_stackoverflow)
SE (1) SE357984B (enrdf_load_stackoverflow)
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US3977061A (en) * 1973-09-17 1976-08-31 Sandvik Aktiebolag Cutting insert and method of making the same
JPS51144389A (en) * 1975-06-09 1976-12-11 Sumitomo Electric Ind Ltd Process for producing hard alloy parts coated with oxygen-containing f ilm
JPS51144388A (en) * 1975-06-09 1976-12-11 Sumitomo Electric Ind Ltd Hard alloy parts coated with multiple layer film
DE2625940A1 (de) * 1975-06-12 1976-12-23 Gen Electric Verfahren zum ueberziehen von hartmetall-produkten
US4019873A (en) * 1975-06-06 1977-04-26 Fried. Krupp Gesellschaft Mit Beschrankter Haftung Coated hard metal body
DE2727250A1 (de) * 1976-06-18 1977-12-29 Sumitomo Electric Industries Oberflaechenbeschichtete sinterhartmetallgegenstaende und ein verfahren zu deren herstellung
DE2725874A1 (de) * 1976-06-16 1977-12-29 Lucas Industries Ltd Spitze fuer einpunkt-drehwerkzeug sowie verfahren zum einpunktdrehen
US4268569A (en) * 1979-02-07 1981-05-19 General Electric Company Coating underlayers
US4282289A (en) * 1980-04-16 1981-08-04 Sandvik Aktiebolag Method of preparing coated cemented carbide product and resulting product
US4284687A (en) * 1978-11-29 1981-08-18 Fried Krupp Gesellschaft Mit Beschrankter Haftung Compound body
US4357382A (en) * 1980-11-06 1982-11-02 Fansteel Inc. Coated cemented carbide bodies
US4399168A (en) * 1980-01-21 1983-08-16 Santrade Ltd. Method of preparing coated cemented carbide product
US4430386A (en) 1979-02-09 1984-02-07 Toyo Kohan Co., Ltd. Composite metal sintered article and method of making same
US4440547A (en) * 1982-05-20 1984-04-03 Gte Laboratories Incorporated Alumina coated silicon nitride cutting tools
US4442169A (en) * 1982-01-28 1984-04-10 General Electric Company Multiple coated cutting tool and method for producing same
DE3303291A1 (de) * 1946-07-17 1984-08-02 Vsesojuznyj naučno-issledovatel'skij instrumental'nyj institut, Moskva Verfahren zur verfestigung von schneidwerkzeugen
US4490191A (en) * 1981-12-16 1984-12-25 General Electric Company Coated product and process
US4525415A (en) * 1981-09-11 1985-06-25 Iscar Limited Sintered hard metal products having a multi-layer wear-resistant coating
USRE32111E (en) * 1980-11-06 1986-04-15 Fansteel Inc. Coated cemented carbide bodies
US4599281A (en) * 1981-12-24 1986-07-08 Schwartzkopf Development Corporation Wearing part
US4696352A (en) * 1986-03-17 1987-09-29 Gte Laboratories Incorporated Insert for a drilling tool bit and a method of drilling therewith
US4749630A (en) * 1983-09-07 1988-06-07 Fried. Krupp Gesellschaft Mit Beschrankter Haftung Coated hardmetal body
EP0403461A1 (en) * 1989-06-16 1990-12-19 Sandvik Aktiebolag Coated cutting insert
US5073411A (en) * 1981-12-16 1991-12-17 Carboloy, Inc. Process for forming a surface oxidized binding layer on hard substrates
US5427843A (en) * 1989-09-08 1995-06-27 Nippon Steel Corporation Ceramic-coated metal sheet
US5487625A (en) * 1992-12-18 1996-01-30 Sandvik Ab Oxide coated cutting tool
US5674564A (en) * 1991-06-25 1997-10-07 Sandvik Ab Alumina-coated sintered body
US5702808A (en) * 1994-11-15 1997-12-30 Sandvik Ab Al2 O2 -coated cutting tool preferably for near net shape machining
US5713133A (en) * 1994-06-27 1998-02-03 Valenite Inc. Methods of preparing cemented metal carbide substrates for deposition of adherent diamond coatings and products made therefrom
US5851687A (en) * 1993-12-23 1998-12-22 Sandvik Ab Alumina coated cutting tool
WO1999061211A1 (en) * 1998-05-26 1999-12-02 Ecer Gunes M Self-sharpening blades and method for making same
EP0999293A1 (en) * 1998-11-05 2000-05-10 Hitachi Metals, Ltd. Aluminium oxide-coated article
US6354008B1 (en) * 1997-09-22 2002-03-12 Sanyo Electric Co., Inc. Sliding member, inner and outer blades of an electric shaver and film-forming method
US20030121158A1 (en) * 2000-02-29 2003-07-03 The Gillette Company, A Delaware Corporation Razor blade technology
US20040172832A1 (en) * 2003-03-04 2004-09-09 Colin Clipstone Razor blade
US20080044242A1 (en) * 2004-08-02 2008-02-21 Boehlerit Gmbh & Co. Kg. Indexable Insert with a Multi-Layer Coating
EP2446988A1 (en) 2010-10-29 2012-05-02 Seco Tools AB Cutting tool insert with an alpha-alumina layer having a multi-components texture
USRE44870E1 (en) 1994-01-14 2014-04-29 Sandvik Intellectual Property Ab Aluminum oxide coated cutting tool and method of manufacturing thereof
US11371150B2 (en) 2020-01-04 2022-06-28 Kennametal Inc. Coating and coated cutting tool comprising the coating

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JPS56152962A (en) * 1980-04-28 1981-11-26 Sumitomo Electric Ind Ltd Coated super hard alloy member
JPS5716161A (en) * 1980-07-02 1982-01-27 Ngk Spark Plug Co Ltd Preparation of coating tip for cutting
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DE3434616C2 (de) * 1983-12-19 1997-06-19 Hartmetall Beteiligungsgesells Verfahren zur Herstellung von Titan-Bor-Oxinitridschichten auf Sinterhartmetallkörpern
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DE3633986A1 (de) * 1985-12-07 1987-06-25 Schmalkalden Werkzeug Oberflaechenschicht auf der basis von aluminiumoxid fuer sinterhartmetallkoerper und verfahren zu ihrer herstellung
JPS6362863A (ja) * 1986-09-02 1988-03-19 Seikosha Co Ltd 金色を呈する物品
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CN110387537B (zh) * 2018-04-20 2021-10-15 北京北方华创微电子装备有限公司 一种原子层沉积设备及气体传输方法

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Cited By (50)

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Publication number Priority date Publication date Assignee Title
DE3303291A1 (de) * 1946-07-17 1984-08-02 Vsesojuznyj naučno-issledovatel'skij instrumental'nyj institut, Moskva Verfahren zur verfestigung von schneidwerkzeugen
US3977061A (en) * 1973-09-17 1976-08-31 Sandvik Aktiebolag Cutting insert and method of making the same
US4019873A (en) * 1975-06-06 1977-04-26 Fried. Krupp Gesellschaft Mit Beschrankter Haftung Coated hard metal body
JPS51144389A (en) * 1975-06-09 1976-12-11 Sumitomo Electric Ind Ltd Process for producing hard alloy parts coated with oxygen-containing f ilm
JPS51144388A (en) * 1975-06-09 1976-12-11 Sumitomo Electric Ind Ltd Hard alloy parts coated with multiple layer film
DE2625940A1 (de) * 1975-06-12 1976-12-23 Gen Electric Verfahren zum ueberziehen von hartmetall-produkten
DE2725874A1 (de) * 1976-06-16 1977-12-29 Lucas Industries Ltd Spitze fuer einpunkt-drehwerkzeug sowie verfahren zum einpunktdrehen
DE2727250A1 (de) * 1976-06-18 1977-12-29 Sumitomo Electric Industries Oberflaechenbeschichtete sinterhartmetallgegenstaende und ein verfahren zu deren herstellung
US4284687A (en) * 1978-11-29 1981-08-18 Fried Krupp Gesellschaft Mit Beschrankter Haftung Compound body
US4268569A (en) * 1979-02-07 1981-05-19 General Electric Company Coating underlayers
US4430386A (en) 1979-02-09 1984-02-07 Toyo Kohan Co., Ltd. Composite metal sintered article and method of making same
US4399168A (en) * 1980-01-21 1983-08-16 Santrade Ltd. Method of preparing coated cemented carbide product
US4282289A (en) * 1980-04-16 1981-08-04 Sandvik Aktiebolag Method of preparing coated cemented carbide product and resulting product
US4357382A (en) * 1980-11-06 1982-11-02 Fansteel Inc. Coated cemented carbide bodies
USRE32111E (en) * 1980-11-06 1986-04-15 Fansteel Inc. Coated cemented carbide bodies
US4525415A (en) * 1981-09-11 1985-06-25 Iscar Limited Sintered hard metal products having a multi-layer wear-resistant coating
US5073411A (en) * 1981-12-16 1991-12-17 Carboloy, Inc. Process for forming a surface oxidized binding layer on hard substrates
US4490191A (en) * 1981-12-16 1984-12-25 General Electric Company Coated product and process
US4599281A (en) * 1981-12-24 1986-07-08 Schwartzkopf Development Corporation Wearing part
US4442169A (en) * 1982-01-28 1984-04-10 General Electric Company Multiple coated cutting tool and method for producing same
US4440547A (en) * 1982-05-20 1984-04-03 Gte Laboratories Incorporated Alumina coated silicon nitride cutting tools
US4749630A (en) * 1983-09-07 1988-06-07 Fried. Krupp Gesellschaft Mit Beschrankter Haftung Coated hardmetal body
US4696352A (en) * 1986-03-17 1987-09-29 Gte Laboratories Incorporated Insert for a drilling tool bit and a method of drilling therewith
EP0403461A1 (en) * 1989-06-16 1990-12-19 Sandvik Aktiebolag Coated cutting insert
US5427843A (en) * 1989-09-08 1995-06-27 Nippon Steel Corporation Ceramic-coated metal sheet
US5674564A (en) * 1991-06-25 1997-10-07 Sandvik Ab Alumina-coated sintered body
US5654035A (en) * 1992-12-18 1997-08-05 Sandvik Ab Method of coating a body with an α-alumina coating
US5487625A (en) * 1992-12-18 1996-01-30 Sandvik Ab Oxide coated cutting tool
US5851687A (en) * 1993-12-23 1998-12-22 Sandvik Ab Alumina coated cutting tool
USRE44870E1 (en) 1994-01-14 2014-04-29 Sandvik Intellectual Property Ab Aluminum oxide coated cutting tool and method of manufacturing thereof
US5713133A (en) * 1994-06-27 1998-02-03 Valenite Inc. Methods of preparing cemented metal carbide substrates for deposition of adherent diamond coatings and products made therefrom
US5702808A (en) * 1994-11-15 1997-12-30 Sandvik Ab Al2 O2 -coated cutting tool preferably for near net shape machining
US5834061A (en) * 1994-11-15 1998-11-10 Sandvik Ab Al2 O3 coated cutting tool preferably for near net shape machining
US6354008B1 (en) * 1997-09-22 2002-03-12 Sanyo Electric Co., Inc. Sliding member, inner and outer blades of an electric shaver and film-forming method
US6389699B1 (en) * 1998-05-26 2002-05-21 Globix Technologies, Inc. Self sharpening blades and method for making same
US6105261A (en) * 1998-05-26 2000-08-22 Globix Technologies, Inc. Self sharpening blades and method for making same
WO1999061211A1 (en) * 1998-05-26 1999-12-02 Ecer Gunes M Self-sharpening blades and method for making same
US6333103B1 (en) 1998-11-05 2001-12-25 Hitachi Metals, Ltd. Aluminum oxide-coated article
EP0999293A1 (en) * 1998-11-05 2000-05-10 Hitachi Metals, Ltd. Aluminium oxide-coated article
US6866894B2 (en) 2000-02-29 2005-03-15 The Gillette Company Razor blade technology
US6684513B1 (en) * 2000-02-29 2004-02-03 The Gillette Company Razor blade technology
US20030121158A1 (en) * 2000-02-29 2003-07-03 The Gillette Company, A Delaware Corporation Razor blade technology
US20040172832A1 (en) * 2003-03-04 2004-09-09 Colin Clipstone Razor blade
US20060265885A1 (en) * 2003-03-04 2006-11-30 The Gillette Company, A Delaware Corporation Razor blade
US20080044242A1 (en) * 2004-08-02 2008-02-21 Boehlerit Gmbh & Co. Kg. Indexable Insert with a Multi-Layer Coating
US8105702B2 (en) * 2004-08-02 2012-01-31 Boehlerit Gmbh & Co. Kg. Indexable insert with a multi-layer coating
EP2446988A1 (en) 2010-10-29 2012-05-02 Seco Tools AB Cutting tool insert with an alpha-alumina layer having a multi-components texture
WO2012055906A2 (en) 2010-10-29 2012-05-03 Seco Tools Ab Alumina layer with multitexture components
US9149871B2 (en) 2010-10-29 2015-10-06 Seco Tools Ab Alumina layer with multitexture components
US11371150B2 (en) 2020-01-04 2022-06-28 Kennametal Inc. Coating and coated cutting tool comprising the coating

Also Published As

Publication number Publication date
GB1394108A (en) 1975-05-14
FR2170383A5 (enrdf_load_stackoverflow) 1973-09-14
BR7207922D0 (pt) 1973-12-13
JPS4859106A (enrdf_load_stackoverflow) 1973-08-18
PL79682B1 (enrdf_load_stackoverflow) 1975-06-30
CA972233A (en) 1975-08-05
DE2253745C3 (de) 1982-01-21
ES408523A1 (es) 1976-02-16
DE2253745A1 (de) 1973-05-17
DE2253745B2 (de) 1975-07-31
JPS5213201B2 (enrdf_load_stackoverflow) 1977-04-13
IT969848B (it) 1974-04-10
SU963450A3 (ru) 1982-09-30
SE357984B (enrdf_load_stackoverflow) 1973-07-16

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