EP0143889A2 - Objet en métal dur revêtu - Google Patents

Objet en métal dur revêtu Download PDF

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Publication number
EP0143889A2
EP0143889A2 EP84109267A EP84109267A EP0143889A2 EP 0143889 A2 EP0143889 A2 EP 0143889A2 EP 84109267 A EP84109267 A EP 84109267A EP 84109267 A EP84109267 A EP 84109267A EP 0143889 A2 EP0143889 A2 EP 0143889A2
Authority
EP
European Patent Office
Prior art keywords
hard
metal
hard metal
material layer
free
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP84109267A
Other languages
German (de)
English (en)
Other versions
EP0143889A3 (fr
Inventor
Udo Dr. König
Hendrikus Dr. Van Den Berg
Norbert Dr. Reiter
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fried Krupp AG
Original Assignee
Fried Krupp AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fried Krupp AG filed Critical Fried Krupp AG
Publication of EP0143889A2 publication Critical patent/EP0143889A2/fr
Publication of EP0143889A3 publication Critical patent/EP0143889A3/fr
Withdrawn legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C30/00Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
    • C23C30/005Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process on hard metal substrates

Definitions

  • the invention relates to a coated hard metal body composed of a hard metal base body containing cobalt and tungsten carbide and a hard metal layer free of binding metal, the hard material layer being composed of hard oxides or of a mixture of hard oxides and hard nitrides or of a mixed crystal of hard oxides and hard nitrides.
  • the invention further relates to a method for producing the coated hard metal body.
  • Hard oxides in particular magnesium oxide, hafnium oxide, chromium (III) oxide and / or aluminum oxide
  • hard nitrides in particular silicon nitride, vanadium nitride, niobium nitride, aluminum nitride, boron nitride, titanium nitride, zirconium nitride, tantalum nitride and / or hafnium nitride, in particular and hard boron
  • Titanium diboride, tantalum diboride or hafnium diboride can be used.
  • the coating of the hard metal part can also consist of mixtures or mixed crystals of the aforementioned hard materials.
  • the hard metal base body of the coated hard metal part proposed in DE-OS 2 233 699 consists of hard metal, which consists of a binding metal and of tungsten carbide, titanium carbide, tantalum carbide and / or niobium carbide is composed.
  • the oxygen-containing hard material layers in particular the hard material layers consisting of oxides, have only insufficient adhesive strength on the hard metal and flake off even with comparatively little stress. There has therefore been no lack of attempts to improve the adhesive strength of the oxygen-containing hard material layers.
  • DE-PS 2 253 745 proposes a cutting insert made of a hard metal base body, an intermediate layer and a binder-free surface layer made of one or more extremely wear-resistant deposits made of aluminum oxide and / or zirconium oxide, in which the intermediate layer consists of one or more carbides and / or nitrides of the elements titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, silicon and / or boron and is free of binding metal.
  • a good bond between the oxidic surface layer and the hard metal base body is to be achieved with the hard metal intermediate layer consisting of carbides and / or nitrides.
  • DE-OS 2 525 185 proposes a wear-resistant molded part which consists of a hard metal base body, an intermediate layer made of one or more borides and an outer layer made of aluminum oxide and / or zirconium oxide.
  • the intermediate boride layer which is composed in particular of the diborides of the elements titanium, zircon, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten, is also intended to improve the adhesive strength of the extremely wear-resistant outer oxidic hard material layer.
  • US Pat. No. 3,261,673 first of all a nickel layer on a tungsten carbide hard metal body to apply and to spray on an aluminum oxide layer, the nickel intermediate layer to achieve better adhesion of the aluminum oxide layer and an improvement in the heat and corrosion resistance of the composite body.
  • the invention has for its object to improve the adhesive strength of binder-free, oxygen-containing hard material layers on hard metal bodies, the application of a separate and some / um thick intermediate layer should be avoided, since the production of the intermediate layer complicates and increases the cost of producing the coated hard metal body.
  • the underlying the invention object is achieved in that the hard metal base body, a 0.2 to 20 / has on its surface by thick zone containing in addition to the hard metal components, the phase CoWB. It is surprising that an extraordinarily good adhesive strength of the oxygen-containing hard material layers is achieved by the incorporation of the CoWB phase into the surface of the hard metal base body, because this phase deteriorates, according to experts, the properties of the hard material-coated hard metal body.
  • the coated hard metal body according to the invention has very good wear properties.
  • the hard material layer has a thickness of 0.2 to 20 / um and consists of aluminum oxide, zirconium oxide or aluminum oxynitride, the nitrogen content of the aluminum oxynitride being 0.1 to 10 atom%. It has surprisingly been found that of the oxide-containing hard material layers, in particular the hard material layers consisting of aluminum oxide, zirconium oxide or aluminum oxynitride have an extraordinarily good adhesive strength on the hard metal base body which has the zone containing CoWB.
  • At least one further binder-metal-free hard material layer made of hard carbides, nitrides, borides and / or oxides of the elements aluminum, silicon, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum is provided on the binder-metal-free hard material layer.
  • tungsten and / or yttrium is applied, wherein the thickness of all the hard coatings / um is 0.5 to 30th
  • the object on which the invention is based is further achieved by a method for producing the coated hard metal body, in which the hard metal base body forms the CoWB-containing zone for 3 to 60 minutes at a temperature of 800 to 1200 ° C., preferably 950 to 1050 ° C. and a pressure of 5000 to 100000 Pascals is treated with a gas mixture of boron trichloride and hydrogen, the partial pressure of the boron trichloride being 1 to 10% of the pressure, then the binder-metal-free hard material layer and then, if appropriate, the further binder-metal-free hard material layers from the gas phase in a known manner be deposited using the CVD process.
  • CoWB phase is formed in one zone by reaction of the boron with the cobalt and tungsten carbide contained in the hard metal, which phase is present in the surface zone along with the other constituents of the hard metal .
  • a residual binder metal content could still be detected in the CoWB-containing zone, while no boron carbide was identified there.
  • up to 66% of the cobalt content of the hard metal base body has passed into the CoWB phase as a result of the reaction with boron, a decrease in the concentration of the CoWB phase naturally occurring within the zone from the outside.
  • the CoWB-containing zone has a boron content of 0.3 to 3% by weight, preferably 0.5 to 2% by weight. Since the boration of the hard metal base body only takes a few minutes, while applying a plurality of / um thick requires Hartstöff interlayer few hours, resulting sich trim process of the invention considerable advantages by saving energy and the furnace chamber.
  • the basic metal body which is provided with a zone containing CoWB, consists of a binder metal phase and a hard material phase.
  • the binder metal phase must contain cobalt and the hard material phase must contain tungsten carbide.
  • the binder metal phase can also contain the binder metals iron and / or nickel, and the hard material phase can also contain the ureas titanium carbide, tantalum carbide and / or niobium carbide in addition to the tungsten carbide.
  • the dimensions of the hard metal base body do not change its dimensions; no boride-containing intermediate layer grows during the boronization. Because of the good wear properties of the coated hard metal body, according to the invention, it should be used as a cutting insert for machining metallic materials, in particular cast steel, since it is particularly suitable for this purpose. has been proven by appropriate investigations.
  • inserts made of a hard metal from the ISO machining application group K10 were introduced, which consisted of 5.5% by weight of cobalt and 94.5% by weight of tungsten carbide.
  • a gas mixture consisting of 1.3% boron trichloride and 98.7% hydrogen was passed through the reactor at a pressure of 40,000 Pascals for 10 minutes.
  • the deposition of a 2 to 3 / um thick layer of aluminum oxide by passing a gas mixture of 2.7% aluminum, 4.3% carbon dioxide, 2.6% hydrogen chloride and 90.4% hydrogen, where the total pressure 6000 Pascal was.
  • the percentages of the individual substances in the two gas mixtures relate to vol.% And at the same time indicate the proportion of the partial pressure of the individual substance to the total pressure.
  • the indexable inserts were removed and subjected to various tests. After the preparation of a metallographic bevel cut, the borated zone and the applied aluminum oxide layer were examined microscopically. There was no chipping of the hard material layer.
  • the hard metal consisting of tungsten carbide grains and the binding metal cobalt showed no changes in the microstructure up to the adjacent aluminum oxide layer. The observation of the structure with the aid of a scanning electron microscope led to the same result.
  • a fine area analysis using an electron beam microsensor found that the surface zone of the hard metal contained about 0.8% by weight of boron in addition to the elements cobalt, tungsten and carbon, the concentration of boron decreasing from the outside in.
  • the CoWB-containing zone had a thickness of approximately 3 to 5 ⁇ m.
  • a composite body was obtained by the process according to the invention, which consisted of a hard metal base body made of tungsten carbide and cobalt with particles of the phase CoWB embedded on its surface and an aluminum oxide layer adhering firmly to it.
  • indexable inserts of the form SNUN 120408 (according to ISO standard) coated in accordance with the invention were subjected to a cutting durability test, the particularly abrasive cast steels GGG 260 HB and hard cast GH 500 being machined on a lathe.
  • commercially available indexable inserts of the same geometry were also tested, which were coated in a known manner with a double layer of titanium carbide and aluminum oxide. The test conditions and results are shown in the table below:
  • the size of the wear was determined in a known manner by measuring the crater depth and the wear mark width. It was found that the composite bodies according to the invention showed only very little wear despite the lower overall thickness of the hard material coating.
  • the indexable inserts were examined using the same methods as described in the first example.
  • the CoWB phase was again found in the edge zone of the hard metal.
  • the X-ray diffraction diagram showed diffraction lines of the phases cobalt, tungsten carbide, mixed carbide, CoWB, aluminum oxynitride and titanium nitride. Electron diffraction also revealed very small amounts of the W 2 Co2 1 B 6 phase, which presumably arises as an intermediate stage in the formation of the CoWB phase.
  • Other phases such as B. Boron carbide, titanium diboride and titanium carbide could not be found.
  • the analyzes thus showed that the composite body consisted of a mixed carbide-containing hard metal with CoWB fractions embedded near the surface and of four successive aluminum oxynitride layers separated by a thin titanium nitride layer or sealed off from the outside.
  • the layer adjacent to the borated hard metal was an aluminum oxynitride layer.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Vapour Deposition (AREA)
  • Cutting Tools, Boring Holders, And Turrets (AREA)
EP84109267A 1983-09-07 1984-08-04 Objet en métal dur revêtu Withdrawn EP0143889A3 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3332260 1983-09-07
DE19833332260 DE3332260A1 (de) 1983-09-07 1983-09-07 Beschichteter hartmetallkoerper

Publications (2)

Publication Number Publication Date
EP0143889A2 true EP0143889A2 (fr) 1985-06-12
EP0143889A3 EP0143889A3 (fr) 1985-09-25

Family

ID=6208456

Family Applications (1)

Application Number Title Priority Date Filing Date
EP84109267A Withdrawn EP0143889A3 (fr) 1983-09-07 1984-08-04 Objet en métal dur revêtu

Country Status (5)

Country Link
US (1) US4749630A (fr)
EP (1) EP0143889A3 (fr)
JP (1) JPS6070179A (fr)
DE (1) DE3332260A1 (fr)
IN (1) IN161226B (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4037480A1 (de) * 1990-11-24 1992-05-27 Krupp Widia Gmbh Verfahren zur herstellung eines beschichteten hartmetallschneidkoerpers
EP0492059A3 (en) * 1990-12-25 1992-09-02 Mitsubishi Materials Corporation Surface coated cermet blade member
DE4110005A1 (de) * 1991-03-27 1992-10-01 Krupp Widia Gmbh Verbundkoerper, verwendung des verbundkoerpers und verfahren zu seiner herstellung
EP0643152A3 (fr) * 1993-09-09 1995-07-26 Plansee Tizit Gmbh Outil de coupe.
US5516588A (en) * 1991-03-27 1996-05-14 Widia Gmbh Composite body, its use and a process for its production

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT387988B (de) * 1987-08-31 1989-04-10 Plansee Tizit Gmbh Verfahren zur herstellung mehrlagig beschichteter hartmetallteile
DE3811907C1 (fr) * 1988-04-09 1989-08-03 Kernforschungszentrum Karlsruhe Gmbh, 7500 Karlsruhe, De
SE464818B (sv) * 1989-06-16 1991-06-17 Sandvik Ab Belagt skaer foer skaerande bearbetning
US5545490A (en) * 1994-06-21 1996-08-13 Mitsubishi Materials Corporation Surface coated cutting tool
US6478887B1 (en) * 1998-12-16 2002-11-12 Smith International, Inc. Boronized wear-resistant materials and methods thereof
US6607782B1 (en) * 2000-06-29 2003-08-19 Board Of Trustees Of The University Of Arkansas Methods of making and using cubic boron nitride composition, coating and articles made therefrom
GB0118755D0 (en) * 2001-08-01 2001-09-26 Univ Leeds Wear resistant boride based coatings
US6767627B2 (en) * 2002-12-18 2004-07-27 Kobe Steel, Ltd. Hard film, wear-resistant object and method of manufacturing wear-resistant object
US8574728B2 (en) * 2011-03-15 2013-11-05 Kennametal Inc. Aluminum oxynitride coated article and method of making the same
US9017809B2 (en) 2013-01-25 2015-04-28 Kennametal Inc. Coatings for cutting tools
US9138864B2 (en) 2013-01-25 2015-09-22 Kennametal Inc. Green colored refractory coatings for cutting tools
US9427808B2 (en) 2013-08-30 2016-08-30 Kennametal Inc. Refractory coatings for cutting tools
US10597784B2 (en) 2017-07-18 2020-03-24 United Technologies Corporation Cold spray nozzle

Family Cites Families (21)

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Publication number Priority date Publication date Assignee Title
GB851208A (en) * 1958-01-17 1960-10-12 Metallgesellschaft Ag Process for the production of titanium boride coatings
US3189477A (en) * 1960-04-13 1965-06-15 Carborundum Co Oxidation-resistant ceramics and methods of manufacturing the same
US3261673A (en) * 1963-05-17 1966-07-19 Norton Co Oxide coated articles with metal undercoat
CH540991A (fr) * 1971-07-07 1973-08-31 Battelle Memorial Institute Procédé pour augmenter la résistance à l'usure de la surface d'une pièce en "métal dur"
SE357984B (fr) * 1971-11-12 1973-07-16 Sandvik Ab
US3804034A (en) * 1972-05-09 1974-04-16 Boride Prod Inc Armor
SE412417B (sv) * 1973-01-18 1980-03-03 Massachusetts Inst Technology Skaerverktyg av volframkarbid och foerfarande foer dess tillverkning
US3955038A (en) * 1973-04-09 1976-05-04 Sandvik Aktiebolag Hard metal body
SE367217B (fr) * 1973-09-17 1974-05-20 Sandvik Ab
AT336905B (de) * 1975-02-10 1977-06-10 Plansee Metallwerk Verschleissteil fur die spanabhebende und spanlose formgebung
DE2525185C3 (de) * 1975-06-06 1986-04-17 Fried. Krupp Gmbh, 4300 Essen Hartmetallkörper
US4018631A (en) * 1975-06-12 1977-04-19 General Electric Company Coated cemented carbide product
SE415199B (sv) * 1977-09-28 1980-09-15 Sandvik Ab Med borerad ytzon forsedd sintrad hardmetallkropp
CH632944A5 (fr) * 1978-06-22 1982-11-15 Stellram Sa Piece d'usure en metal dur.
US4268582A (en) * 1979-03-02 1981-05-19 General Electric Company Boride coated cemented carbide
JPS55154562A (en) * 1979-05-18 1980-12-02 Sumitomo Electric Ind Ltd Sintered hard alloy part for base material of surface-covered tool material and their manufacture
JPS55154564A (en) * 1979-05-18 1980-12-02 Sumitomo Electric Ind Ltd Lamination-covered sintered hard alloy parts
DD144930B1 (de) * 1979-07-20 1984-11-14 Voigt Klaus Dr Ing Verfahren zur herstellung von diffusionsgebundenen doppelschichten
CA1174438A (fr) * 1981-03-27 1984-09-18 Bela J. Nemeth Procede de fabrication de corps en carbure fritte enrichi d'agglomerant
US4343865A (en) * 1981-06-24 1982-08-10 General Electric Company Hard metal body and method of making same
US4447263A (en) * 1981-12-22 1984-05-08 Mitsubishi Kinzoku Kabushiki Kaisha Blade member of cermet having surface reaction layer and process for producing same

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4037480A1 (de) * 1990-11-24 1992-05-27 Krupp Widia Gmbh Verfahren zur herstellung eines beschichteten hartmetallschneidkoerpers
EP0492059A3 (en) * 1990-12-25 1992-09-02 Mitsubishi Materials Corporation Surface coated cermet blade member
DE4110005A1 (de) * 1991-03-27 1992-10-01 Krupp Widia Gmbh Verbundkoerper, verwendung des verbundkoerpers und verfahren zu seiner herstellung
US5516588A (en) * 1991-03-27 1996-05-14 Widia Gmbh Composite body, its use and a process for its production
EP0643152A3 (fr) * 1993-09-09 1995-07-26 Plansee Tizit Gmbh Outil de coupe.

Also Published As

Publication number Publication date
US4749630A (en) 1988-06-07
JPS6070179A (ja) 1985-04-20
EP0143889A3 (fr) 1985-09-25
IN161226B (fr) 1987-10-24
DE3332260A1 (de) 1985-03-28

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Inventor name: KOENIG, UDO, DR.

Inventor name: VAN DEN BERG, HENDRIKUS, DR.

Inventor name: REITER, NORBERT, DR.