EP0149449B1 - Corps en métal dur, en particulier outil tranchant en métal dur - Google Patents

Corps en métal dur, en particulier outil tranchant en métal dur Download PDF

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Publication number
EP0149449B1
EP0149449B1 EP84890252A EP84890252A EP0149449B1 EP 0149449 B1 EP0149449 B1 EP 0149449B1 EP 84890252 A EP84890252 A EP 84890252A EP 84890252 A EP84890252 A EP 84890252A EP 0149449 B1 EP0149449 B1 EP 0149449B1
Authority
EP
European Patent Office
Prior art keywords
coating
hard
metal body
layer
body according
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.)
Expired
Application number
EP84890252A
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German (de)
English (en)
Other versions
EP0149449A1 (fr
Inventor
Johann Ing. Kiefer
Oskar Dr. Pacher
Johann Dipl.-Ing. Stamberger
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.)
Vereinigte Edelstahlwerke AG
Original Assignee
Vereinigte Edelstahlwerke AG
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Publication of EP0149449A1 publication Critical patent/EP0149449A1/fr
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Publication of EP0149449B1 publication Critical patent/EP0149449B1/fr
Expired legal-status Critical Current

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Classifications

    • 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

Definitions

  • the invention relates to a hard metal body, in particular a hard metal cutting tool, with a coating based on carbides and / or nitrides of elements from IV.
  • Such tools are used primarily in the machining of materials, in particular metalworking.
  • Use A large number of coated hard metal bodies with a base body and mostly multi-layer coatings are known, but there is always the endeavor to achieve high cutting speeds with as little wear as possible and also to have a tool available which can also withstand high mechanical stresses, such as those with an interrupted one Occur cut, withstands. All efforts are aimed at still increasing the service life of the tools and the ease of machining. So z. B.
  • such phenomena should be reduced if care is taken to ensure that oxygen introduction is avoided at least in certain areas of the base body coating by first providing the base body with a carbide-nitride or carbonitride layer, Then diffusion from the substrate into the layer or vice versa takes place, which is followed by a highly wear-resistant coating with oxide. Before this oxidic layer is applied, the intermediate coating can be oxidized from the outside in order to improve the adhesion, but only in a layer thickness that does not reach the substrate.
  • a multi-layer coating is also known from EU-A-0 083 842, in which a binding layer made of carbide or oxycarbide compounds is oxidized on the surface and bears an oxidic wear layer.
  • the surface oxidation of the binding layer is intended to improve the adhesive strength of the oxidic outer layer, an intermediate layer between the binding layer and the substrate also being proposed.
  • Such bodies can admittedly have a wear layer adhering firmly to the binding layer, in the binding layer itself or in the zones on the substrate surface, brittle layers arise in particular as a result of the oxygen diffusion when subjected to thermal stress, which layers adversely affect the performance properties of the tools.
  • a coating is made known which is formed from homogeneous individual layers with an alternating composition, whereby the thermal stresses are to be reduced and the wear resistance is to be increased. If the individual layers are applied alternately with up to seven intermediate layers, flaking of the coating can occur in practical use due to the resulting stress.
  • Patent Abstracts of Japan, unexamined applications, Field C, Volume 6, No. 186, September 22, 1982; The Patent Office Japanese Government, page 7 C 126; Kokai no. 57-98 670 (Sumitomo) has become known a cutting tool made of coated hard metal, in which one or more titanium compounds are applied to a substrate, on which there is an outer layer made of A1 2 0 3 .
  • the titanium compound (s) consists of a titanium oxide, the oxygen being partially replaced by carbon and nitrogen. At higher working temperatures, in particular due to oxygen diffusion, intermediate layers of this type lead to brittle layer regions which favor the chipping of the cover layer, in particular on the substrate, as a result of which the service life of the tool is reduced.
  • the invention relates to a hard metal body, in particular a hard metal cutting tool, of the type mentioned at the outset, which is characterized in that a first coating formed from one or more layers with at least one 0.1 to 2.5 atom% is formed directly on the substrate of the basic body.
  • the above-mentioned inclusions have at least substantial proportions of metal boride.
  • the body can optionally be heat treated and / or compacted.
  • the oxycarbide, carbonitride or nitride - particularly preferred oxycarbonitride - of the first coating has an aluminum content of 0.5 to 2 atomic% and an oxygen content of 1 to 5 atomic%, this is particularly reliable adhesion guaranteed both coatings, it should be noted that even with zirconium oxide-containing second coating aluminum alone is able to bring the beneficial effect.
  • the first coating has two or more layers of oxycarbide, oxycarbonitride or oxynitride, preferably oxycarbonitride, at least one of the above-mentioned elements, the aluminum content of the individual layers being one of them directly on the substrate bordering layer is rising away to the outside.
  • the oxygen content with concentrations of 0.1 to 8 atom%, preferably 1 to 5 atom%, of the oxycarbide, oxycarbonitride or oxynitride layer (s) of the first coating has no adverse effect.
  • the first coating comprises two or more layers with an oxycarbide or oxycarbonitride or oxynitride, preferably has oxycarbonitride, at least one of the above-mentioned elements, the oxygen content of the individual layers increasing outwards from the layer directly adjacent to the substrate, with even better operating behavior being achievable if the oxygen content in the first coating is different layer directly adjacent to the substrate, preferably substantially linearly increasing. Very thin individual layers can also be present, so that the increase is practically continuous.
  • the oxidic coating it is advantageous if it or at least some of its layers have or have zirconium of 1 to 20% by weight, preferably 2 to 15% by weight.
  • the second coating has two or more oxide layers
  • the zirconium content of the individual layers increasing outwards from a layer which may be zirconium-free and which immediately adjoins the first coating, can be removed among others estimate the abrasion on the surfaces subject to wear and thus the remaining tool life, whereby an essentially linear - gradual or continuous - increase in the zirconium content is particularly favorable in this respect.
  • unintentional downtimes can be largely avoided.
  • the doping of the first coating or of its layers with aluminum itself has a stabilizing effect, so that the presence of zirconium is not urgent per se, the oxidic layer of the second coating immediately adjacent to the first coating can therefore also have a zirconium-free layer with aluminum oxide.
  • a further substantial increase in wear resistance can be achieved if the boride-containing inclusions provided in the second coating are those with aluminum and / or zirconium boride.
  • a particularly intimate yet improved bond between the individual layers of the coatings can be achieved in particular by heat treatment or by means of hot pressing to be advantageously provided.
  • a body according to the invention is therefore particularly preferred if the substrate and layer (s) of the first and second coating each have diffusion zones with one another.
  • the invention further relates to a method for producing hard metal bodies, in particular cutting tool bodies, as described so far, the body optionally being subjected to heat or heat treatment, preferably thermal diffusion treatment, in particular at temperatures from 900 to 1600 ° C., preferably from 1100 to 1500 ° C. and / or a post-compression process, preferably an isostatic hot pressing, in particular at pressures of 500 to 2500 bar.
  • heat or heat treatment preferably thermal diffusion treatment, in particular at temperatures from 900 to 1600 ° C., preferably from 1100 to 1500 ° C. and / or a post-compression process, preferably an isostatic hot pressing, in particular at pressures of 500 to 2500 bar.
  • Cuts made of hard metal (85% WC, 9.5% TiC + TaC, 5.5% Co) are heated in a furnace under protective gas or vacuum to a temperature of 1000 ° C, and then for 60 minutes with a gas mixture with 5 % TiCl 4 , 80% H 2 , 5% N 2 , 5% CH 4 and 5% CO treated. Then the gas mixture AICI 3 is mixed in amounts of 0.5% (test series 1a) and 1% (test series 1b) with small amounts of CO (2% each) based on AICI 3 .
  • the total pressure in the furnace is 150 mbar during the treatments. After a treatment period of 210 minutes, an approximately 3 ⁇ m thick, completely dense oxycarbonitride layer was formed, which, in each case on average in the case of the test series 1a with 0.5 atom% AI and in those of the test series 1 with 1.4 Atom% AI was doped.
  • Cuts made of hard metal (91% WC, 2.5% TiC + TaC, 6.5% Co) are heated in an oven under protective gas or vacuum to a temperature of 1000 ° C and then for 40 minutes with a gas mixture with 8% TiCl 4, 2% ZrCl4, 70% hydrogen, 15% N 2 and 5% C0 2 initially (experiment A) treated. Thereafter is replaced at intervals of 10 min each for 5 min the TiC1 4 by AICI 3 and continuously 2 content of the C0 2 content is increased from 5 to 15% under the corresponding reduction of the H.
  • the total pressure in the furnace during this treatment is 650 mbar. After 90 minutes there was an approximately 2.5 ⁇ m thick oxynitride layer in which the Al content was 0.9 atomic% on average and the oxygen content from the substrate to the outside from 0.5 to 3.5 atoms -% increase, trained.
  • test series 2a and 2b were maintained.
  • the coated material obtained contained no aluminum in its hard material layer.
  • Cuts made of hard metal (79% WC, 10% TiC + TaC, 11% Co) are heated in a furnace under protective gas or vacuum to a temperature of 1020 ° C, and then for 90 minutes with a gas mixture with 5% TiCl 4 , Treated 70% H 2 and 25% CH 4 .
  • the working pressure in the furnace is 200 mbar.
  • the temperature is then increased to 1050 ° C. and at a working pressure of 150 mbar, 5% AICI 3 and 5% CO 2 are then added alternately for 5 minutes to the gas mixture for 120 minutes, each time with a corresponding reduction in the hydrogen content.
  • test series 3a After a total duration of 150 min, a coating was formed in test series 3a which had an Al content of 1.5 atom% AI and 6 atom% oxygen enriched against the outer surface, while Al and the oxygen were close to the substrate -Content below 0.1 atom%.
  • Cutting bodies according to the preceding examples and test series are treated in a gas mixture with 10% AICI 3 , 80% H 2 , 5% CO 2 and 5% ZrCl 4 for 120 min at a temperature of 1020 ° C, during which period at regular intervals of 8 min the proportion of CO 2 is reduced in each case for 2 minutes and replaced by BCl 3 .
  • Oxidic coatings are formed on the cutting bodies, which have embedded borides of aluminum or zirconium.
  • Cutting bodies according to the preceding examples and test series are treated in a gas mixture with initially 10% AlCl 3 , 70% hydrogen, 12% CO 2 , 5% ZrCl 4 and 3% HCl at 1030 ° C and a working pressure of 200 mbar in such a way that the AlCl 3 content is continuously reduced to 60% of the initial value over a period of 150 min and at the same time the ZrCl 4 content is increased accordingly, so that the total AlCl 3 + ZrCl 4 remains constant.
  • An approximately 2 ⁇ m thick layer with an outer zone rich in Zr0 2 is obtained.
  • the flexibility of the layers and their adhesion that can be achieved by installing Al in the base layer is particularly positive.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Cutting Tools, Boring Holders, And Turrets (AREA)

Claims (16)

1. Corps en métal dur, en particulier outil de coupe en métal dur, avec un revêtement à base de carbures et/ou de nitrures d'éléments du IVème au Vlème groupe secondaire du Tableau Périodique, et avec au moins un autre revêtement à base d'oxyde d'aluminium et/ou d'oxyde de zirconium, caractérisé en ce qu'est appliqué directement sur le substrat du corps de base un premier revêtement, constitué d'une ou plusieurs couches, avec au moins une couche, comportant de 0,1 à 2,5 % en atomes d'aluminium et de 0,1 à 8,0 % en atomes d'oxygène, d'oxycarbure, d'oxycarbonitrure ou d'oxynitrure d'au moins l'un des éléments Ti, Zr, Hf, V, Nb, Ta et Cr, revêtement sur lequel est disposé un deuxième revêtement d'oxydes, constitué d'une ou plusieurs couches d'oxyde d'aluminium et/ou de zirconium.
2. Corps en métal dur selon la revendication 1, caractérisé en ce que le premier revêtement comporte au moins deux couches d'oxycarbure, oxycarbonitrure ou oxynitrure, de préférence oxycarbonitrure, d'au moins l'un des éléments mentionnés dans la revendication 1, la teneur en aluminium des différentes couches augmentant vers l'extérieur à partir d'une couche en contact direct avec le substrat.
3. Corps en métal dur selon l'une des revendications 1 et 2, caractérisé en ce que la teneur en aluminium des couches du premier revêtement augmente d'une manière essentiellement linéaire, vers l'extérieur, à partir de la couche en contact direct avec le substrat.
4. Corps en métal dur selon l'une des revendications 1 à 3, caractérisé en ce que le premier revêtement comporte au moins deux couches d'un oxycarbure ou d'un oxycarbonitrure ou d'un oxynitrure, ou d'un carbonitrure, d'au moins l'un des éléments mentionnés dans la revendication 1, la teneur en oxygène des différentes couches augmentant vers l'extérieur à partir de la couche en contact direct avec le substrat.
5. Corps en métal dur selon l'une des revendications 1 à 4, caractérisé en ce que la teneur en oxygène des couches du premier revêtement augmente d'une manière essentiellement linéaire vers l'extérieur à partir de la couche en contact direct avec le substrat.
6. Corps en métal dur selon l'une des revendications 1 à 5, caractérisé en ce que la ou les couches du deuxième revêtement contiennent de 1 à 20 % en poids de zirconium.
7. Corps en métal dur selon l'une des revendications 1 à 6, caractérisé en ce que le deuxième revêtement comporte au moins deux couches d'oxyde, la teneur en zirconium des différentes couches augmentant vers l'extérieur à partir de la couche, éventuellement exempte de zirconium, en contact direct avec le premier revêtement.
8. Corps en métal dur selon l'une des revendications 1 à 7, caractérisé en ce que la couche d'oxyde du deuxième revêtement, en contact direct avec le premier revêtement, est une couche d'oxyde d'aluminium exempte de zirconium.
9. Corps en métal dur selon l'une des revendications 1 à 8, caractérisé en ce que, dans le deuxième revêtement, la teneur en zirconium augmente d'une manière essentiellement linéaire vers l'extérieur à partir de la couche d'oxyde en contact direct avec le premier revêtement.
10. Corps en métal dur selon l'une des revendications 1 à 9, caractérisé en ce que la couche d'oxyde, ou au moins une couche du deuxième revêtement, présente des insertions contenant un borure.
11. Corps en métal dur selon l'une des revendications 1 à 10, caractérisé en ce que les insertions contenant un borure, présentes au moins dans une couche du deuxième revêtement, sont formées de borure(s) d'aluminium et/ou de zirconium.
12. Corps en métal dur selon l'une des revendications 1 à 11, caractérisé en ce que le corps est soumis à un traitement thermique.
13. Corps en métal dur selon l'une des revendications 1 à 12, caractérisé en ce que le corps est compacté.
14. Corps en métal dur selon l'une des revendications 1 à 13, caractérisé en ce que le substrat et la ou les couches du premier et du deuxième revêtements présentent des zones de diffusion.
15. Procédé pour la préparation d'un corps en métal dur selon l'une des revendications 1 à 14, caractérisé en ce qu'on utilise un traitement thermique à des températures de 900 à 1600°C et/ou un traitement thermique pendant l'opération de revêtement.
16. Procédé selon la revendication 15, caractérisé en ce qu'on utilise une opération de recompression à des pressions de 500 à 2500 bar.
EP84890252A 1983-12-22 1984-12-20 Corps en métal dur, en particulier outil tranchant en métal dur Expired EP0149449B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AT4494/83 1983-12-22
AT449483A AT385947B (de) 1983-12-22 1983-12-22 Hartmetallkoerper, insbesondere hartmetall-schneidwerkzeug

Publications (2)

Publication Number Publication Date
EP0149449A1 EP0149449A1 (fr) 1985-07-24
EP0149449B1 true EP0149449B1 (fr) 1988-05-18

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EP84890252A Expired EP0149449B1 (fr) 1983-12-22 1984-12-20 Corps en métal dur, en particulier outil tranchant en métal dur

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EP (1) EP0149449B1 (fr)
AT (1) AT385947B (fr)
DE (1) DE3471279D1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008026358A1 (de) * 2008-05-31 2009-12-03 Walter Ag Werkzeug mit Metalloxidbeschichtung

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FI862725A0 (fi) * 1986-06-26 1986-06-26 Ahlstroem Oy Slitfast haolplatta.
AT387186B (de) * 1987-05-04 1988-12-12 Ver Edelstahlwerke Ag Beschichteter hartmetallkoerper
US5449547A (en) * 1993-03-15 1995-09-12 Teikoku Piston Ring Co., Ltd. Hard coating material, sliding member coated with hard coating material and method for manufacturing sliding member
US7264668B2 (en) * 2001-10-16 2007-09-04 The Chinese University Of Hong Kong Decorative hard coating and method for manufacture
DE10320652A1 (de) * 2003-05-07 2004-12-02 Kennametal Widia Gmbh & Co.Kg Werkzeug, insbesondere Schneidwerkzeug und Verfahren zur CVD-Abscheidung einer zweiphasigen Schicht auf einem Substratkörper
DE102010039035A1 (de) * 2010-08-06 2012-02-09 Walter Ag Schneidwerkzeug mit mehrlagiger Beschichtung

Family Cites Families (8)

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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
DE2851584B2 (de) * 1978-11-29 1980-09-04 Fried. Krupp Gmbh, 4300 Essen Verbundkörper
DE3069238D1 (en) * 1979-12-28 1984-10-25 Ver Edelstahlwerke Ag Hard body, especially hard metal wearing part, and process for its production
EP0032887B1 (fr) * 1980-01-21 1986-07-23 Sandvik Aktiebolag Procédé pour la fabrication d'un produit en carbure aggloméré ayant un revêtement, et produit ainsi obtenu
EP0083842B1 (fr) * 1981-12-16 1989-07-12 Carboloy Inc. Elément en métal dur revêtu et procédé de sa fabrication
AT377786B (de) * 1981-12-24 1985-04-25 Plansee Metallwerk Verschleissteil, insbesondere hartmetall -schneideinsatz zur spanabhebenden bearbeitung
US4416670A (en) * 1982-05-20 1983-11-22 Gte Laboratories Incorporated Carbide coated composite silicon nitride cutting tools

Non-Patent Citations (1)

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Title
PATENT ABSTRACTS OF JAPAN, unexamined applications, Field C Band 7, Nr. 77, 30. März 1983 THE PATENT OFFICE JAPANESE GOVERNMENT Seite 9 C 159 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008026358A1 (de) * 2008-05-31 2009-12-03 Walter Ag Werkzeug mit Metalloxidbeschichtung

Also Published As

Publication number Publication date
EP0149449A1 (fr) 1985-07-24
AT385947B (de) 1988-06-10
DE3471279D1 (en) 1988-06-23
ATA449483A (de) 1987-11-15

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