WO2018130628A1 - Procédé pour le traitement d'une surface d'un corps en métal dur et pour le revêtement du corps en métal dur traité par une couche de diamant - Google Patents

Procédé pour le traitement d'une surface d'un corps en métal dur et pour le revêtement du corps en métal dur traité par une couche de diamant Download PDF

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Publication number
WO2018130628A1
WO2018130628A1 PCT/EP2018/050706 EP2018050706W WO2018130628A1 WO 2018130628 A1 WO2018130628 A1 WO 2018130628A1 EP 2018050706 W EP2018050706 W EP 2018050706W WO 2018130628 A1 WO2018130628 A1 WO 2018130628A1
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Prior art keywords
carbon
phase
hard metal
surface zone
cemented carbide
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PCT/EP2018/050706
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German (de)
English (en)
Inventor
Manuel MEE
Original Assignee
Baden-Württemberg Stiftung Ggmbh
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Priority to EP18700483.3A priority Critical patent/EP3568503A1/fr
Publication of WO2018130628A1 publication Critical patent/WO2018130628A1/fr

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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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/02—Pretreatment of the material to be coated
    • 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
    • C23C16/0209—Pretreatment of the material to be coated by heating
    • C23C16/0218—Pretreatment of the material to be coated by heating in a reactive atmosphere
    • 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
    • C23C16/274—Diamond only using microwave discharges
    • 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
    • C23C28/324—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 matrix material layer comprising a mixture of at least two metals or metal phases or a metal-matrix material with hard embedded particles, e.g. WC-Me
    • 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
    • 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
    • C23C28/341—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
    • 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
    • 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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
    • C23C8/10—Oxidising
    • C23C8/12—Oxidising using elemental oxygen or ozone
    • 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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
    • C23C8/20—Carburising
    • 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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/80—After-treatment

Definitions

  • the present invention relates to a method for treating a surface of a cemented carbide body and to a method for coating a treated cemented carbide body with at least one diamond layer.
  • the hard metal body may in particular be a component with a complex geometry, such as a milling cutter or a drill.
  • the invention is therefore preferably used in the cutting industry, especially in the processing of highly abrasive materials. However, other applications are also conceivable in principle.
  • Carbide tools are widely used in the industry for machining materials such as metals or composites, for example, when machining or milling.
  • Carbide is generally used as a material in the metal-cutting industry.
  • a stamina of the hard metal can be increased enormously by a coating.
  • diamond is used as a coating, in particular because of its outstanding hardness.
  • the hard metal mostly comprises tungsten carbide in combination with cobalt.
  • the cobalt may adversely affect an adhesion action between a surface of the tool and the diamond layer.
  • cobalt which binds tungsten carbide in the cemented carbide, can promote formation of sp 2 bonded carbon by interaction with the coating process or with diamond.
  • a requirement for a stressed hard metal tool material can be, in particular, a symbiosis of the material properties of hardness and toughness, which can be found in the
  • a pressed mixture of tungsten carbide and cobalt granules can be heated to temperatures between 1350 ° C and 1500 ° C and thereby compressed. This can contribute to a good wetting behavior of the liquefied cobalt, in particular by penetrating into the interstices of the tungsten carbide grains and filling them.
  • the hard metal may mostly comprise cobalt.
  • the cobalt may diffuse to a surface due to a required temperature, which is typically between 700 ° C and 1000 ° C, and interact with the already synthesized diamond. In this case, a formation of, or a conversion to sp 2-bonded carbon can be forced and thus adversely affect an adhesion effect between the surface of the hard metal body and the diamond.
  • EP 0 519 587 B1 describes a process for coating a cobalt-sintered tungsten carbide substrate with a diamond film comprising the steps of first removing a small amount of tungsten carbide from a selected portion of the surface of an unpolished cobalt sintered tungsten carbide substrate, wherein the cobalt-binding metal is obtained substantially intact; Removing any residue left as a result of performing the first step and removing a small amount of the binder metal from the surface of this unpolished substrate; Depositing a substantially continuous diamond film on said selected portion of the surface of said unpolished substrate.
  • EP 1 042 527 B1 describes a coated cemented carbide body with at least one wear-resistant CVD or PVD layer.
  • This body contains up to 12% by weight of binder phase of at least one of the elements Co, Ni and Fe.
  • the body contains a surface zone B1 having a thickness of 5 to 50 ⁇ m, which contains essentially triangular WC platelets for which the texture coefficient ratio TCR (100: 001)> 1.75, preferably> 2.0, more preferably> 2, 5 and most preferably> 3.0.
  • TCR texture coefficient ratio
  • hard coatings are described which are investigated for their suitability as diamond growth intermediate layers
  • the diamond deposition was performed by hot wire activated vapor deposition.
  • a sufficient density of crystallization nuclei could only be achieved by pretreatment by means of ultrasound with diamond powder. be enough.
  • the density of crystallization nuclei also depends on interlayer materials and the substrate temperature.
  • the determined densities of nuclei were containing the titanium and silicon interlayers 10 5 -10 8 cm "2 In Petrikowski et al, Study of CrN and NbC inter layers for HFCVD diamond deposition Onto WC-Co substrate, In:.. Diamond and Related Materials 33 (2013), pp. 38-44, describe deposition of chromium nitride (CrN x ) and niobium carbide (NbC) by magnetron sputtering on cobalt-sintered tungsten carbide substrates, and diamond deposition by hot-wire activated vapor deposition
  • CrNx and NbC interlayers were deposited at various substrate temperatures, in particular at 400, 550 and 700 ° C.
  • the stability of these interlayers for diamond deposition was achieved by heat treatment in H 2 atmosphere for 60 hours at a temperature of 765 ° C in the hot wire activated gas phase deposition reactor.
  • WO 00/31314 A1 describes a coated body which has a substrate of tungsten, carbon and cobalt and in which the substrate has a surface.
  • An eta phase is present on the surface of the substrate.
  • Fibrous tungsten carbide grains are present on the surface of the substrate.
  • the surface of the substrate has a surface roughness Ra greater than about 12 microinches.
  • On the surface of the substrate is a coating layer.
  • Also described is a method of making a coated body comprising the steps of: providing a substrate comprising tungsten, carbide and cobalt and the substrate having at least one eta-phase surface thereon; Subjecting the substrate to an eta phase on the surface of a conversation treatment at a temperature of between about 1250 ° C and about 2000 ° C under at least a partial vacuum for a time sufficient to convert at least a portion of the eta phase to fibrous tungsten carbide grains wherein the fibrous tungsten carbide grains are at the surface, whereby the substrate surface has a surface roughness Ra greater than 12 microinches; and applying a coating to the surface of the substrate.
  • DE 698 29 076 T2 describes a body made of hard metal which is provided with at least one wear-resistant layer.
  • the body contains a zone in the cemented carbide and adjacent to the applied layer, the triangular WC plates with a spe- contains specific orientation. Different binder phase gradients are possible.
  • the body is particularly suitable for applying CVD diamond layers.
  • DE 697 10 242 T2 discloses that at least the surface area of a tungsten carbide cutting tool substrate is carburized in a cobalt matrix to chemically passivate the cobalt thereon prior to depositing a diamond film thereon.
  • the passivation improves adhesion by preventing the reaction of the cobalt with the diamond during the deposition process.
  • cobalt is removed from the exposed surfaces of the tungsten carbide grains by heat treatment in inert gas or by hydrogen plasma.
  • DE 10 2007 058 484 A1 describes a method for applying a multilayer coating to workpieces and / or materials.
  • the method comprises the following steps: application of a support layer to the workpiece or the material by thermal spraying or plasma spraying; Application of an adhesion-promoting intermediate layer and application of a carbon- or silicon-containing cover layer by plasma evaporation.
  • a surface of a cemented carbide body is to be stabilized and structured. to reduce diffusion of a binder metal during a diamond coating of the cemented carbide body and to improve a specific adhesion of the diamond layer on the cemented carbide body surface. In particular, this is intended to increase the service life of the cemented carbide body.
  • the terms “having”, “having”, “including” or “including” or any grammatical variations thereof are used in a non-exclusive manner. Accordingly, these terms may refer to situations in which, in addition to the features introduced by these terms, there are no other features or to situations in which one or more other features are present.
  • the terms "at least one” and “one or more” and grammatical variations of these terms when used and to be used in connection with one or more elements or features, are intended to provide the element or feature in a single or multiple way can usually be used only once, for example, at the first introduction of the feature or element. In a subsequent re-mention of the feature or element, the corresponding term “at least one” or “one or more” is generally no longer used, without limiting the possibility that the feature or element may be single or multiple.
  • a method for treating a surface of a cemented carbide body, in particular for preparation prior to application of a diamond coating is proposed.
  • the method here comprises the method steps, which are described in detail below.
  • the procedural steps can be carried out in particular in the predetermined order. However, another order is also conceivable.
  • one or more method steps can be performed simultaneously or temporally overlapping.
  • one, several or all of the method steps can be performed simply or repeatedly.
  • the method may additionally comprise further method steps.
  • the method comprises the following steps:
  • the cemented carbide body is provided in step a).
  • the term "hard metal body” is to be understood as meaning in principle any body which has at least one hard metal at least on a part of a surface. Hard metals can have very high hardness, high wear resistance and high hardness.
  • the hard metal body comprises at least one carbide phase of a metal of the 4th to 6th subgroup of the periodic table and at least one binder metal.
  • the term "carbide phase” refers to a carbide compound of the metals of groups 4 to 6 of the Periodic Table, in particular titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten
  • the carbide body may comprise at least one further carbide compound, for example titanium carbide and / or tantalum carbide Other compounds are also conceivable in principle
  • the carbide compound may be referred to in particular as a reinforcing phase
  • the binder metal may in particular serve as a matrix, as a binder and / or as a toughness component of the cemented carbide body played by Cobalt.
  • the tungsten carbide can be used as the hard material phase in a proportion of 70% to 99% and particularly preferably in a proportion of 80% to 96%, and cobalt as binder metal in a proportion of 1% to 30%, particularly preferably 4% to 20%.
  • the tungsten carbide may preferably be in the form of tungsten carbide grains.
  • the tungsten carbide grains can in particular a mean diameter of 0.1 ⁇ to 10 ⁇ , preferably from 0.2 ⁇ to 6 microns. Other dimensions are also conceivable.
  • the cobalt can in particular fill in interspaces of the tungsten carbide grains.
  • treatment of a surface basically refers to any physical and / or chemical process by means of which a surface of any body is changed or modified.Therefore, physical and / or chemical properties of the treated body differ after carrying out the treatment Treatment, in particular of a treated surface of the body, of physical and / or chemical properties of the body before the treatment is carried out
  • the treated surface of the treated body may in particular have a chemical composition and / or a surface structure which differs from a chemical composition and / or a surface structure of the body prior to treatment.
  • the cemented carbide body can be placed in a quartz housing and / or placed before the implementation of further process steps.
  • the quartz housing can be configured, for example, as a quartz tube or as a quartz dome.
  • the quartz housing may in particular have at least one wall, which may have a distance between 1 mm and 100 mm, preferably 5 mm and 80 mm, particularly preferably between 10 mm and 40 mm to an axis and / or a surface of the hard metal body.
  • the quartz housing may in particular be suitable for carrying out one or more plasma treatments, as described below. In this case, the plasma can be limited in particular to the immediate environment of the component to be treated by the quartz housing.
  • the hard metal body can be treated in an inert atmosphere, in particular in a hydrogen atmosphere, in particular heated, for example to temperatures of greater than 500 ° C.
  • heating generally refers to any process in which a medium, for example a gaseous medium, a liquid medium and / or a medium of a mixture of a gaseous medium with a liquid medium, is heated or heated
  • Atmosphere is to be understood in particular as an atmosphere under which a chemical reaction between potential reactants under given conditions does not occur or occurs only to a negligible extent.
  • the heating can be carried out in particular via an interaction with a plasma.
  • at least one plasma treatment can be used, in particular an H 2 plasma treatment and / or an N 2 plasma treatment.
  • plasma may in particular designate a mixture of particles at an atomic-low molecular level, the constituents of which are partially charged components, in particular ions and / or electrons.
  • the plasma may therefore comprise free charge carriers,
  • a plasma may be completely immersed in ions and electrons. This is referred to as complete ionization, but depending on particle densities, temperatures, and fields of relative strength, such as electric, magnetic, and / or gravitational fields, plasmas may behave completely differently, provided that a neutral particle component exists.
  • plasma treatment basically refers to a process in which any object over a period of time, in particular exposed to a plasma over a defined period of time.
  • chemical reactions can be supported by the plasma, in particular by high concentrations of chemically reactive molecular fragments.
  • other applications are conceivable in principle.
  • step b) the low-carbon ternary phase is formed in a surface zone of the cemented carbide body.
  • step b) may comprise the following steps:
  • the carbide phase may in particular comprise at least one tungsten carbide compound.
  • step b1) may comprise forming at least one tungsten oxide compound in the surface zone by treatment of the cemented carbide body, and step b2) may comprise reducing the tungsten oxide compound.
  • Step b1) and step b2) can each be carried out as separate method steps.
  • Step b1) and b2) can preferably be carried out in each case by means of at least one plasma treatment.
  • step b1) can be carried out in an oxidative atmosphere. Sphere be performed and during step b2) in a reducing atmosphere, for example hydrogen and / or nitrogen occurs.
  • step b1) and step b2) may be performed within a single process step.
  • oxygen can be added to an existing hydrogen and / or nitrogen atmosphere for a limited time.
  • step b1) a decarburization of the surface zone, ie a depletion of carbon can take place.
  • carbon can be removed from the surface zone.
  • W0 3 and / or CoW0 4 can form in the surface zone of the cemented carbide body.
  • the term "surface zone” basically designates a segment of any object which extends from a surface of the object into an interior of the object
  • the surface zone may in particular extend from the surface of the cemented carbide body over an area into an interior of the cemented carbide body
  • the surface zone may have a thickness of 0.01 ⁇ m to 300 ⁇ m, preferably of 0.1 ⁇ m to 200 ⁇ m, and particularly preferably of 1 ⁇ m to 100 ⁇ m.
  • step b2) the at least one tungsten oxide compound can be reduced, wherein a low-carbon ternary phase is formed in the surface zone.
  • reducing basically refers to any partial chemical reaction in which electrons are taken up by a particle, such as an atom, ion or molecule, whereby the oxidation number of the particle becomes smaller
  • reduce oxygen removal from oxides present here, step b2) can be carried out in particular by means of at least one H 2 plasma treatment, one N 2 plasma treatment and / or one H 2 / N 2 plasma treatment.
  • the term "low-carbon ternary phase” denotes a carbide compound of the carbide-phase metal of the fourth to sixth subgroups of the periodic table, the binder metal and of carbon
  • the low-carbon ternary phase may have the stoichiometry of M 6 C or of M 12 C, where M is the sum of the carbide-phase metal atoms present in the carbide compound and the binder metal, because of the low carbon content, the term “low-carbon” may be used for the present ternary phase.
  • the low-carbon ternary phase comprises the elements tungsten, cobalt and carbon and is therefore commonly used. referred to as "eta phase".
  • the elements tungsten, cobalt and carbon can be present in different stoichiometries.
  • M may be selected from the group consisting of tungsten, cobalt, iron, nickel.
  • Co 6 W 6 C, Co 3 W 3 C or W 4 Co 2 C may be present.
  • the low-carbon ternary phase can therefore be, in particular, a brittle mixed carbide which can greatly reduce the flexural strength of an object.
  • the formation of the low-carbon ternary phase can be effected by a removal of carbon from the surface zone of the cemented carbide body.
  • steps b1) and b2) can be carried out in the form of two separate method steps.
  • step b1) at temperatures of at least 400 ° C, preferably at least 500 ° C, preferably at least 600 ° C, preferably at least 700 ° C, preferably at least 800 ° C, preferably at least 900 ° C, preferably at least 1000 ° C and especially preferably at least 1 100 ° C are performed.
  • temperatures above 1100 ° C. can have a process-accelerating effect.
  • step b1) can be carried out in an oxidative atmosphere.
  • the oxidative atmosphere may be pure oxygen.
  • the oxidative atmosphere may comprise oxygen in bound form, for example H 2 O, OH " , CO and / or CO 2
  • steps b1) and b2) may be carried out by means of at least one plasma treatment
  • step b2) can be carried out by means of at least one H 2 plasma treatment and / or one N 2 plasma treatment
  • step b2) can be particularly preferred at temperatures of at least 1000 ° C., preferably of at least 1100 ° C. of at least 1200 ° C, are performed.
  • steps b1) and b2) can be carried out within a single process step, in particular by means of a hydrogen plasma treatment, during which the oxygen is supplied.
  • the hydrogen plasma treatment can be carried out in particular at a temperature of at least 1000 ° C., preferably at a temperature of at least 1200 ° C., particularly preferably at a temperature of at least 1300 ° C.
  • the carbon can preferably be supplied by way of a carbon-containing compound via an outer surface into the surface zone, preferably via a gas phase, particularly preferably via a plasma, in particular via a microwave plasma.
  • supply refers to any process in which at least one medium, in particular a fluid medium, in particular a gaseous medium, comes into proximity and / or in contact with another medium or object. Be referred to.
  • outer surface refers in particular to any surface of the cemented carbide body which faces an environment of the cemented carbide body.
  • the cobalt is thereby converted into a gas phase in the surface zone, while recrystallized grains of the carbide phase form within the surface zone.
  • the cobalt is thus subsequently present in the interparticle spaces between the recrystallized grains of the carbide phase, both in the form of a cobalt wetting on the outer surface of the surface zone, and further in the low carbon ternary phase.
  • the term "wetting" in the context of the present invention basically refers to a propagation of a material in the form of a film on any surface of an element., Step c) may in particular comprise an enrichment of the low-carbon ternary phase with carbon.
  • the surface zone can be supplied with carbon via the outer surface, preferably via a carbon-containing compound, preferably via the gas phase and particularly preferably via a plasma.
  • Step c) can therefore also be referred to as recarbonization.
  • carbon can be supplied, preferably via a gas phase.
  • the carbon can preferably be provided by means of at least one hydrocarbon precursor, in particular by means of methane (CH 4 ) or ethyne (C 2 H 2 ).
  • CH 4 methane
  • ethyne C 2 H 2
  • Other hydrocarbon precursors are also conceivable.
  • Step c) may in particular be carried out at a time when the oxygen is completely or at least almost completely removed from the surface during the reduction phase and the low-carbon ternary phase is present in the surface zone, or at a time at which the low-carbon ternary phase has sufficient volume that contributes to a reformation of the surface during the recarbonization.
  • step c) recrystallized grains of the carbide phase are formed within the surface zone.
  • the term "grain” basically refers to a part of a polycrystalline structure
  • the grain is generally also referred to as crystallite polycrystalline structure may differ in particular in an orientation of a crystal structure.
  • the term "grain boundary” basically denotes a two-dimensional lattice defect
  • the grain boundary can separate regions, in particular the grains or crystallites of different orientation, with otherwise identical crystal structure, from one another
  • the recrystallized grains can be, for example, prisms with a triangular and / or hexagonal
  • the prisms may comprise tungsten
  • recarbonization preferably almost complete recarbonization, and most preferably complete recarbonization, may be to stoichiometric tungsten carbide while in a deeper region of the surface zone a stoichiometric formation of tungsten carbide has not yet been completed, the remaining cobalt may be in the form of a cobalt wetting of the outer surface of the surface zone as well as bound in the remaining low-carbon ternary phase in the inter-granular spaces in the deeper region of the surface zone.
  • a gradient of carbon stored in tungsten can be generated within the surface zone.
  • the term "gradient" refers in particular to a gradient or an increase of any size or parameter between two locations, in particular a concentration gradient between the two locations, where a first concentration of a substance at a first location differs from one location
  • the gradient may be directed downwards from the outer surface of the cemented carbide body into the interior of the cemented carbide body
  • a first concentration of intercalated carbon in the tungsten grains at or near the outer surface may be greater than a second concentration of carbon in the interior of the cemented carbide body occurs and therefore the low carbon ternary phase remains in the grain boundaries, while on the outer surface is the cobalt wetting, the cobalt can wet especially existing there tungsten carbide grains.
  • the outer surface may be wetted with the binder metal.
  • the tungsten carbide grains may be wetted with cobalt.
  • wetting can not be achieved by gas-assisted evaporation. can be removed since chemical bonding of the tungsten carbide grains to the cobalt does not permit this.
  • the low-carbon ternary phase is converted into interparticle spaces of the crystallized grains in a surface region of the surface remote from the surface into a binding metal-stabilizing phase.
  • the binder metal stabilizing phase basically refers to a phase which fixes the binder metal and at least partially restricts its surface-directed diffusion.
  • the cobalt stabilizing phase for the binder metal comprises tungsten, in particular cobalt tungstate COWO 4 The conversion takes place from the low-carbon, tertiary phase in the form of the eta phase to cobalt tungstate by selective oxidation.
  • oxidation refers to a chemical reaction in which an atom, ion or molecule gives off electrons, thereby increasing an oxidation number
  • oxidation can include the formation of an oxygen-containing compound, in particular CoW0 4 , W0 3 and /
  • selective oxidation refers to oxidization that affects cobalt wetting on the outer surface and the low-carbon ternary phase in the surface zone, while recarbonized tungsten is unaffected by oxygen in the plasma.
  • the selective oxidation of the low-carbon ternary phase can be carried out in particular by means of at least one plasma treatment.
  • at least one gas can be used, selected from the group consisting of: hydrogen, oxygen.
  • gases are also conceivable.
  • at least one gas flow can be used, wherein the gas flow in a standard cubic centimeter per minute (sccm) can be specified. Regardless of pressure and temperature, this unit can be used to describe a defined amount of flowing gas per unit of time.
  • a gas mixture of H 2 and O 2 can be used, in particular in a ratio of 6: 1. in principle are also other conditions conceivable, for example, the gas mixture in a ratio of 1: 1 to 20: 1 inclusive.
  • the plasma treatment in step d) can be carried out in particular at a temperature of from 400 ° C. to 1500 ° C., preferably from 700 ° C. to 1100 ° C., and particularly preferably at a temperature above 900 ° C. Furthermore, the plasma treatment, for example, over a period in the range of 1 s to 200 s, preferably from 2 s to 150 s and more preferably carried out from 5 s to 120 s. In a particularly preferred embodiment, the method can have at least one further step:
  • a "primer layer” in the context of the present invention is basically a layer of at least one substance which produces a close physical and / or chemical bond in an interface with a surface of any element
  • the adhesion promoter layer may in particular be designed to avoid a reduction of cobalt tungstate during the diamond coating.
  • the adhesion promoter layer may in particular comprise a silicon oxycarbonitride layer (a-SiOCN) and / or a silicon oxycarbide layer (a-SiOC).
  • a-SiOCN silicon oxycarbonitride layer
  • a-SiOC silicon oxycarbide layer
  • any layers are conceivable in the production of which interactions with cobalt tungstate are avoided, which are thermally stable and which have a good bond to cobalt and / or to a diamond coating, which will be described in more detail below.
  • the primer layer itself can inhibit the diffusion of cobalt.
  • the silicon oxycarbonitride layer and / or the silicon oxycarbide layer may in particular be an amorphous silicon oxycarbonitride layer.
  • the term "amorphous" refers in particular to a property of any substance in which atoms of the substance do not have ordered structures but form an irregular pattern
  • the substance can have a short order, but usually no long-range order
  • the adhesion promoter layer can preferably be obtained by means of at least one plasma treatment be applied to the surface of the hard metal body the plasma treatment is a microwave plasma treatment. This treatment step may be carried out by means of at least one gas selected from the group consisting of: nitrogen, oxygen, tetramethylsilane (TMS).
  • a ratio of gas flows from nitrogen to oxygen and TMS may in particular be from 10 to 50 sccm for nitrogen, from 2 to 30 sccm for oxygen and from 0.5 to 3sccm for TMS, preferably 30 sccm for nitrogen, 10 sccm for oxygen and 1 , 5 for TMS.
  • the term "sccm" refers here to a standard cubic centimeter per minute
  • the microwave plasma treatment can be carried out over a period of 15 seconds to 300 seconds, preferably from 20 seconds to 100 seconds and particularly preferably from 20 seconds to 60 seconds Layer thickness of 10 nm, preferably from 100 nm, up to 500 nm, preferably up to 300 nm.
  • a method for coating a treated cemented carbide body with at least one diamond layer is proposed.
  • the method may comprise the method steps which are described below.
  • the method steps may preferably be carried out in the predetermined order.
  • the two method steps can be performed in particular at different locations in succession, simultaneously or overlapping in time.
  • one or both process steps can be carried out simply or repeatedly.
  • the method may additionally comprise further method steps.
  • the method for coating a hard metal body with at least one diamond layer comprises the following steps:
  • diamond layer may refer to any layer of diamond on a surface of an object, the term “diamond” referring in particular to a cubic modification of the carbon.
  • Diamond usually forms octahedron-shaped crystals. Other observed forms are the tetrahedron, dodecahedron and the Cube.
  • a macroscopic structure of the diamond layer which may in particular be a fine-crystalline diamond layer, can vary widely.
  • the application of the diamond layer can preferably be effected by means of at least one CVD method, in particular by means of a microwave plasma.
  • CVD method basically refers to a chemical vapor deposition in which a solid is deposited due to a chemical reaction from a gas phase on a surface of any substrate.
  • the method for coating a hard metal body can be carried out in particular in the quartz housing, as has already been described or will be described below.
  • the quartz housing may in particular have a geometry which at least partially corresponds to a geometry of the hard metal body, which is designed, for example, as a milling cutter or drill. This may be particularly advantageous in order to ensure a homogeneous plasma treatment and / or diamond coating.
  • the steps of the above-listed methods may preferably be carried out in a coherent process, particularly preferably in a microwave plasma.
  • the steps can preferably be carried out without removing the cemented carbide body from the coating installation in the meantime and / or without aerating the coating installation in the meantime. Consequently, contamination of the outer surface of the cemented carbide body can be avoided or at least reduced.
  • a treated cemented carbide body is proposed.
  • the treated cemented carbide body is made by the method of treating a surface of a cemented carbide body as already described or described below.
  • a cemented carbide body coated with at least one diamond layer is proposed.
  • the cemented carbide body coated with the diamond layer is produced by the method for coating a cemented carbide body, as has already been described or will be described below.
  • the proposed devices and the proposed methods have numerous advantages over known devices and methods.
  • the method for treating a surface of a hard metal body post-diffusion of cobalt can be at least largely prevented.
  • the primer layer may increase an increase in specific adhesion between the cemented carbide body and the diamond layer, especially when cobalt or cobalt oxide wetting is present on the surface. As a result, an adhesion of the diamond layer on the coated cemented carbide body can be significantly improved.
  • step d) of the method according to the invention for producing a coated hard body very short process cycles are possible.
  • a microwave plasma can be used.
  • An advantage of the microwave plasma can be, in particular, that all method steps are possible in a cohesive process and a process duration can thus be significantly reduced compared to conventional methods.
  • a hardness and toughness of the surface zone of the hard metal body can be improved and thus a service life of the hard metal body can be extended.
  • Such a coated tool can be used thereby longer. Adhesion of diamond to the cemented carbide body can be ensured.
  • a microwave plasma in sequential order a stabilizing and structuring of the surface of the hard metal body, in particular by recrystallization of the surface zone achieved, a diffusion of cobalt through an intergranular imple- mented CoW0 4 -Diffusionsbarriere at least substantially prevented, and specific adhesion to the diamond layer via the adhesive layer , in particular via the silicon oxycarbonitride coating.
  • complex geometries can be pretreated and coated. While so far the plasma can occupy a relatively large space, this can be avoided by a quartz housing close to the component.
  • the method according to the invention for producing a coated cemented carbide body can furthermore have simple transferability to different carbide types.
  • even complex components can be coated with diamond.
  • a complete pre-treatment routine and a subsequent coating can be combined into a coherent process.
  • FIGS. 1 A to 1 F show a method according to the invention for treating a surface of a cemented carbide body, wherein the cemented carbide body is shown in each case as a cross section;
  • FIG. 2 shows a method according to the invention for coating a treated cemented carbide body with at least one diamond layer, wherein the cemented carbide body is represented as a cross section;
  • FIG. 3 shows an exemplary quartz housing in a cross-sectional representation;
  • FIG. 4 shows roughness average values for differently pretreated hard metal samples
  • FIGS. 5A and 5B quantify cobalt post-diffusion over a period of 3
  • FIG. 6 shows an evaluation of a marginal zone hardness by means of Vickers hardness measurement
  • FIG. 7 shows an evaluation of a Weibull statistics fracture toughness by acoustic crack detection during indentation with a Rockwell indenter
  • FIGS. 8A and 8B show a schematic representation of a notch test (FIG. 8A) and a graphical illustration of a feed path taking into account different material treatments (FIG. 8B).
  • FIGS. 1A to 1 E show a method according to the invention for treating a surface 110 of a cemented carbide body 12.
  • the cemented carbide body 12 is shown in each case as a cross section.
  • the hard metal body 1 12 is provided.
  • the hard metal body 12 may comprise at least one tungsten carbide compound.
  • the hard metal body 12 may comprise at least 70%, in particular at least 87%, tungsten carbide.
  • the hard metal body 1 12 include cobalt as a binder metal.
  • the hard metal body 1 12 have at least one further element, such as nickel and / or iron.
  • other embodiments are conceivable in principle.
  • At least one low-carbon ternary phase is formed in a surface zone 14 of the hard-metal body 12.
  • a decarbonization ie a depletion of carbon
  • the surface zone 1 14 may in particular be a segment 1 16 of the hard metal body 1 12, which extends from the surface 1 10 over an area 1 18 in an interior 120 of the hard metal body 1 12.
  • the surface zone 1 14 may have a thickness d of 0.5 ⁇ m to 100 ⁇ m.
  • the method step according to FIG. 1B can be carried out in particular by means of at least one heat treatment and / or plasma treatment.
  • temperatures of at least 400 ° C, preferably of at least 500 ° C, preferably of at least 600 ° C, preferably of at least 700 ° C, preferably of at least 800 ° C, preferably of at least 900 ° C, preferably of at least 1000 ° C. and more preferably at least 1 100 ° C are used.
  • this process step can be carried out in an oxidative atmosphere.
  • a further substep as shown in FIG.
  • the at least one tungsten oxide compound is reduced, forming a low-carbon ternary phase Co x W y C in the surface zone 14.
  • bound oxygen can be removed.
  • the partial step according to FIG. 1C can be carried out in particular by means of at least one plasma treatment, in particular by means of at least one H 2 plasma treatment and / or one N 2 plasma treatment.
  • this process step can be carried out at temperatures of at least 1000 ° C., preferably of at least 1200 ° C. and more preferably of at least 1300 ° C.
  • carbon is preferably supplied to the cemented carbide body 12 via a carbon-containing compound via an outer surface 122 into the surface zone 14.
  • the carbon-containing compound can be supplied, for example, by means of at least one hydrocarbon precursor, in particular by means of methane.
  • the carbon-containing compound can be supplied via a gas phase.
  • the cobalt is consequently at least partially, ie completely or partially, released in the surface zone 1 14 and evaporated. The remaining cobalt may thus be present in the form of a cobalt wetting 124 on the outer surface 122 of the surface zone 14.
  • the cobalt bound in the low carbon ternary phase is present in interparticle spaces of the recrystallized grains in a surface remote region 128 of the surface zone.
  • crystallized grains of the carbide phase can form. Furthermore, within the surface zone 14, a gradient of carbon stored in tungsten can be generated. In particular, the gradient may be directed downwardly from the outer surface 122 into the interior 120 of the cemented carbide body 122. This is shown schematically with an arrow 126. Thus, a first concentration of carbon at or near the outer surface 122 may be greater than a second concentration of carbon in the interior 120 of the hard metal body 1 12. In this way, incompletely recarbonated tungsten may still be surrounded by the low carbon ternary phase becomes.
  • the binding metal cobalt stabilizing phase may in particular be adapted to prevent further diffusion of the cobalt from the hard metal body 1 12 and the surface zone 1 14 over the surface 110 of the surface zone 14.
  • the process step according to FIG. 1 E can be carried out by means of a selective oxidation of the eta phase.
  • the selective oxidation of the low-carbon ternary phase can be carried out in particular by means of at least one plasma treatment, in particular in an atmosphere of hydrogen and oxygen.
  • the plasma treatment can be carried out in particular at a temperature of at least 200 ° C., preferably of at least 300 ° C., preferably of at least 600 ° C. and more preferably of at least 900 ° C.
  • the plasma treatment can be carried out, for example, over a period in the range of 5 s to 120 s.
  • the hard metal body 1 12 can also be referred to as a treated hard metal body 130 after the method step according to FIG.
  • an adhesion promoter layer 134 in particular a silicon oxycarbonitride layer, is applied to at least part of the outer surface 122.
  • the adhesion promoter layer 134 may be, in particular, an amorphous silicon oxycarbonitride layer 136.
  • the adhesion promoter layer 134 can be applied to a treated surface 138 of the cemented carbide body 12, for example, by means of at least one plasma treatment.
  • the plasma treatment may be a microwave plasma treatment.
  • the microwave plasma treatment can be carried out by means of at least one gas selected from the group consisting of: nitrogen, hydrogen, oxygen, tetramethylsilane.
  • FIG. 2 shows a method according to the invention for coating a treated cemented carbide body 130 with at least one diamond layer 132 in cross-section.
  • the method according to FIG. 2 furthermore comprises carrying out the method steps of the method for treating a surface 110 of a cemented carbide body 12, as illustrated, for example, in FIGS. 1A to 1F.
  • FIGS. 1A to 1F For further details, reference may therefore be made to the description of FIGS. 1A to 1F.
  • the process step which is shown in Figure 2, may follow the process steps according to the figures 1 A to 1 F.
  • At least one diamond layer 132 is applied to at least one part 140 of the treated surface 138 of the hard metal body 12.
  • the diamond layer 132 may be applied to a primer layer surface 142 of the primer layer 134.
  • the application of the diamond layer 132 can be effected by means of at least one CVD method, in particular by means of a microwave plasma.
  • FIG. 3 shows an exemplary quartz housing 146 in a cross-sectional view.
  • the quartz housing can enclose the hard metal body 12.
  • the hard metal body 1 12 may be a milling cutter 148, for example.
  • the quartz housing 146 may in particular have at least one wall 150 which does not exceed a distance a between 1 mm and 100 mm, preferably 5 mm and 80 mm, particularly preferably between 10 mm and 40 mm, relative to an axis 152 of the hard metal body 1 12.
  • the quartz housing 1 12 may be particularly suitable for carrying out one or more plasma treatments of the method according to FIGS. 1A to 1 F and FIG. 2.
  • FIG. 4 shows arithmetic mean roughness values R a determined for a differently pretreated hard metal sample with a profilometer.
  • the method of treating a surface of a cemented carbide body may restructure the surface. This can promote a mechanical interlocking of the diamond layer and the hard metal body and have a decisive influence on a later layer adhesion of the diamond layer.
  • polished hard metal bodies reference number 1 with a mean WC grain size of 0.6 ⁇ m, a roughness Ra of 0.01 ⁇ m was determined.
  • the maximum achievable R a value when using the wet-chemical method according to EP 0 519 587 B1 on a hard metal body of the same type is about 0.3 ⁇ m (reference number 2).
  • FIG. 5A shows the determined cobalt postdiffusion during a diamond coating routine over a period of 3 hours for different surface pretreatment. ments. Surfaces II and III produced as a result of surface pretreatment were further characterized by XRD analysis. The respective spectra can be seen in FIG. 5B, the upper spectrum for surface II and lower spectrum for surface III. ( Figure 5B).
  • thermosetting treatment of the diamond layer 132 largely takes place via a surface structuring and can thus be based on an increase in the surface area of the cemented carbide body 12, a layer interlocking and mechanisms of crack deflection and branching , Due to a finding that even after the thermochemical treatment, the surface 1 10 is wetted by cobalt, a specific adhesion of the diamond layer 132 on the treated hard metal body 130 may be limited. In addition, it has been shown that the surface 110 can be contaminated with post-diffusing cobalt even before the conclusion of coalescence of diamond grains.
  • An intention of the method of treating a surface of a cemented carbide body may therefore be, based on the thermal surface treatment, to reduce influences of a cobalt-diamond interaction and to significantly increase the specific adhesion.
  • post-diffusion cobalt is shown for a period of 3 hours for different surface pretreatments.
  • Reference number I denotes an untreated sample
  • reference number II denotes a sample after carrying out process steps a-b2
  • reference number III denotes a sample after carrying out process steps a-b1
  • reference number IV denotes a sample after carrying out process steps a) -e ).
  • Co-back diffusion was quantified by X-ray spectroscopy (EDX) using a silicon-doped DLC coating, which can act as a capture layer.
  • EDX X-ray spectroscopy
  • the appropriately pretreated specimen was provided with the DLC layer and then exposed to the conditions of a three-hour diamond coating process.
  • the cobalt can accumulate in the DLC layer and then be comparatively quantified via the depth information of an EDX signal, as is done in FIG. 5A.
  • FIG. 6 shows an evaluation of a marginal zone hardness H by means of Vickers hardness measurement in accordance with the standard DIN EN ISO 6507-1: 2005 to -4: 2005 for a test load of 100 kiloponds, abbreviated to "HV100.”
  • the sample provided with reference number 1 acts it is reference numeral 2 denotes a sample of etched cemented carbide body, and reference numeral 3 denotes a cemented carbide body after performing steps a) to c).
  • the edge zone stability is strongly influenced by the wet-chemical process; the WC structure can collapse under the applied force due to the lack of cohesion in connection with the high porosity due to lack of cobalt binder.
  • Figure 7 shows an evaluation of fracture toughness by Weibull statistics by acoustic crack detection. For this purpose, during an indentation with a defined force ramp and Rockwell indenter, the occurrence of the first crack above a given triggering threshold was detected. For this purpose, a polished, but otherwise untreated sample (reference number 2) was compared with a sample which was treated according to process steps a) -c) (reference number 3). The latter shows a much lower probability of failure V with respect to the polished substrate at a certain load K.
  • the Weibull modulus of 32.9 ⁇ 5.5 is a factor of 3 greater than the modulus of the polished sample with a value of 1 1, 4 ⁇ 2.2, correspondingly lower is the spread of the measured values.
  • the characteristic strength is assigned a probability of failure of 63.2% and for the treated sample is also clearly above the value of the untreated sample.
  • FIGS. 8A and 8B show a schematic representation of a notch test (FIG. 8A) and a graphical representation of a feed path taking into account different material treatments (FIG. 8B).
  • a notch test was performed.
  • a ceramic of silicon-infiltrated silicon carbide (SiSiC) was used as the workpiece 154. Due to its inhomogeneous structure, the workpiece 154 should represent a process in which wear due to surface disruption is important.
  • the workpiece 154 was designed in particular as a round rod 156.
  • the speed n was 1 180 rpm, the step speed v c at 30 m / min, the feed rate v, at 0.1 mm / min and the feed rate v f at 0 mm / min.
  • Indexable inserts 158 were used, which were each coated with a CVD diamond layer with a layer thickness of 5 ⁇ .
  • a shape of the indexable insert and the stepping speed were chosen such that a thermally induced wear was at least largely suppressed.
  • the workpiece 154 was scored accordingly.
  • a notch 160 is shown. After defined delivery paths of 100 ⁇ m, a cutting edge 162 was evaluated in each case. In general, when performing a notch test, a layer delamination may occur or abrasive wear may occur until a layer is worn through.
  • FIG. 8B shows a graphical representation of a feed path taking into account different material treatments.
  • Material treatment "A” corresponds to a sample without pretreatment and without coating
  • Material treatment "B” corresponds to a wet-chemical pretreatment according to US 5 236 740 A
  • material treatment “C” corresponds to a material treatment according to the present invention
  • the respective delivery distances ZW are in ⁇ These can be defined in particular by the fact that either the diamond layer was delaminated or was rubbed off by an abrasive wear, while the samples of the material treatment "C” could be found to have a service life of 3.2 times at a given infeed speed. No layer delamination could be detected with respect to sample "B” It could be further determined that wear was continuous by abrasion and it was also found that a service life with a layer thickness was scaled.

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Abstract

L'invention concerne un procédé pour le traitement d'une surface (110) d'un corps en métal dur (112). Le procédé comprend les étapes suivantes : a) utilisation d'un corps en métal dur (112), le corps en métal dur (112) comprenant au moins une phase de carbure d'un métal du 4ème au 6ème groupe secondaire du système périodique et au moins un métal liant ; b) formation d'au moins une phase ternaire pauvre en carbone, comprenant le métal de la phase de carbure, le métal liant et du carbone, dans une zone de surface (114) du corps en métal dur (112) ; c) apport de carbone via une surface externe (122) dans la zone de surface (114), le métal liant dans la zone de surface (114) étant au moins partiellement transformé en phase gazeuse et des grains recristallisés de la phase de carbure se formant dans la zone de surface (114), le métal liant passant dans un mouillage (124) de la surface externe (122) de la zone de surface (114) et se trouvant sous forme liée dans la phase ternaire pauvre en carbone dans des espaces intermédiaires entre les grains recristallisés dans une zone (128) éloignée de la surface de la zone de surface (114) ; d) transformation de la phase ternaire pauvre en carbone dans des espaces intermédiaires entre les grains recristallisés dans une zone (128) éloignée de la surface de la zone de surface (114) dans une phase stabilisant le métal liant ; une surface traitée (138) du corps en métal dur (112) étant obtenue. L'invention concerne en outre un procédé pour le revêtement d'un corps en métal dur (130) ainsi traité par au moins une couche de diamant (132).
PCT/EP2018/050706 2017-01-13 2018-01-12 Procédé pour le traitement d'une surface d'un corps en métal dur et pour le revêtement du corps en métal dur traité par une couche de diamant WO2018130628A1 (fr)

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DE102017200543.2A DE102017200543A1 (de) 2017-01-13 2017-01-13 Verfahren zur Behandlung einer Oberfläche eines Hartmetallkörpers und zur Beschichtung des behandelten Hartmetallkörpers mit einer Diamantschicht

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WO2021252488A1 (fr) 2020-06-08 2021-12-16 Halia Therapeutics, Inc. Inhibiteurs de la kinase nek7

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CN111286717A (zh) * 2019-12-26 2020-06-16 兰州空间技术物理研究所 一种类富勒烯碳基复合薄膜及其制备方法
CN111286717B (zh) * 2019-12-26 2022-06-03 兰州空间技术物理研究所 一种类富勒烯碳基复合薄膜及其制备方法
WO2021252488A1 (fr) 2020-06-08 2021-12-16 Halia Therapeutics, Inc. Inhibiteurs de la kinase nek7

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