EP3031948B1 - Body coated with hard material - Google Patents

Body coated with hard material Download PDF

Info

Publication number
EP3031948B1
EP3031948B1 EP15185878.4A EP15185878A EP3031948B1 EP 3031948 B1 EP3031948 B1 EP 3031948B1 EP 15185878 A EP15185878 A EP 15185878A EP 3031948 B1 EP3031948 B1 EP 3031948B1
Authority
EP
European Patent Office
Prior art keywords
layer
hard
layers
coated body
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.)
Revoked
Application number
EP15185878.4A
Other languages
German (de)
French (fr)
Other versions
EP3031948A1 (en
Inventor
Hendrikus Van Den Berg
Hartmut Westphal
Volkmar Sottke
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.)
Kennametal Inc
Original Assignee
Kennametal Inc
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=40586932&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP3031948(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Kennametal Inc filed Critical Kennametal Inc
Priority to PL15185878T priority Critical patent/PL3031948T3/en
Publication of EP3031948A1 publication Critical patent/EP3031948A1/en
Application granted granted Critical
Publication of EP3031948B1 publication Critical patent/EP3031948B1/en
Revoked legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/24Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24942Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
    • Y10T428/2495Thickness [relative or absolute]
    • Y10T428/24967Absolute thicknesses specified
    • Y10T428/24975No layer or component greater than 5 mils thick

Definitions

  • the invention relates to a hard-coated body with a plurality of CVD applied hard material layers.
  • the cutting material should be resistant to abrasion, which at an early stage has led to hard metal or cermet substrate bodies being provided with surface coatings, with carbides, nitrides or carbonitrides of titanium and later aluminum oxide layers being used as wear protection layers.
  • hard metal or cermet substrate bodies being provided with surface coatings, with carbides, nitrides or carbonitrides of titanium and later aluminum oxide layers being used as wear protection layers.
  • multi-layer wear protection layers of different hard materials As wear-reducing layers, for example, aluminum oxide layers are known, which are arranged on one or more intermediate layers such as titanium carbonitride or titanium nitride.
  • Ti-Al-N layer which can be produced as a monophase layer with aluminum contents up to 60% by means of PVD. At higher aluminum contents, however, a mixture of cubic and hexagonal TiAlN is formed, and with even higher proportions of aluminum only the softer and not wear-resistant hexagonal wurtzite structure is formed.
  • PVD plasma CVD
  • plasma CVD requires high plasma homogeneity because the plasma power density has a direct impact on the Ti / Al atomic ratio of the layer.
  • the production of single-phase cubic Ti 1-x Al x N layers with a high aluminum content is not possible with the industrially used PVD processes.
  • WO 2007/003648 A1 in order to improve the wear resistance and the oxidation resistance, it is proposed to produce a hard-coated body with a single or multilayer coating system by CVD containing at least one Ti 1-x Al x N hard material layer, including the body in a reactor at temperatures in the range of 700 ° C to 900 ° C is coated by CVD without plasma excitation and are used as precursors titanium halides, aluminum halides and reactive nitrogen compounds, which are mixed at elevated temperature.
  • the chlorine content is in the range between 0.05 to 0.9 At%. It is also known from this document that the Ti 1-x Al x N hard material layer or layers up to 30% by mass amorphous layer components may contain.
  • the hardness value of the layers obtained is in the range of 2,500 HV to 3,800 HV.
  • the layer system applied to a substrate body consists of a titanium nitride, titanium carbonitride or titanium carbide bonding layer applied to the body, followed by a phase gradient layer and finally an outer layer of a single- or multi-phase Ti 1-x Al x N hard-material layer.
  • the phase gradient layer consists of a TiN / h-AlN phase mixture on its side facing the connection layer and, with increasing layer thickness, has an increasing phase fraction of fcc-TiAIN with a proportion of more than 50% and, concomitantly, a simultaneous decrease in the phase proportions of TiN and h- AlN on.
  • the thermal resistance of the coating is of great importance for the application of this material in machining operations, in particular at high cutting speeds.
  • temperatures are clearly above 1000 ° C. At such temperatures, different coefficients of expansion that exist for the substrates between the individual layers, significantly. This leads to the formation of stresses between the individual layers and, if the high temperature is transported by heat conduction from the outer layer to the substrate body, in the worst case to a detachment of the coating, making the cutting insert is unusable.
  • Ti 1-x Al x N, Ti 1-x Al x C or Ti 1-x Al x CN layer instead of a TiCN layer commonly used in the prior art has the advantage that the thermal conductivity in the layer disposed below the Al 2 O 3 layer is about 80% smaller, so that the Ti 1-x Al x N, Ti 1-x Al x C or Ti 1-x Al x CN layer as significantly improved thermal isolation to the substrate body proves.
  • the outer Al 2 O 3 layer is also more resistant to oxidation and harder by about 50% compared to a TiCN outer layer, resulting in a higher wear resistance.
  • the Ti 1-x Al x CN, Ti 1-x Al x C or Ti 1-x Al x N layer may be single-phase and have a cubic structure, or be multi-phase, and another phase in addition to a cubic main phase Wurtzit für and / or TiN have. Up to 30 mass% may contain amorphous layer constituents. The chlorine content is between 0.01 to 3 At%.
  • a TiN and / or TiCN layer can be used as a bonding layer to the substrate body, which consists of a hard metal, a cermet or a ceramic, so that the sequence of layers from inside to outside TiN or TiCN TiAlC (N) -Al 2 O 3 is.
  • TiCN layers are also present between the Al 2 O 3 outer layer and the Ti 1-x Al x N layer, Ti 1-x Al x C layer or the Ti 1-x Al x CN layer possible.
  • the aluminum content as metal content is preferably between 70% and 90%.
  • the layer thickness of a Ti 1-x Al x N layer, Ti 1-x Al x C layer or a Ti 1-x Al x CN layer may be between 2 ⁇ m to 10 ⁇ m, preferably 3 ⁇ m to 7 ⁇ m, vary.
  • the aforementioned layer may also contain proportions of hexagonal aluminum nitride, at most 25%.
  • Ti 1-x Al x N Ti 1-x Al x C
  • Ti 1-x Al x CN Ti 1-x Al x CN
  • the TiAlN / TiAlCN / TiAlC alternating layer then has a total thickness resulting from the sum of the thicknesses of each individual layer, which is between 1 nm to 5 nm.
  • the total thickness should be at least 1 micron to 5 microns.
  • the TiAlN, TiAIC or TiAICN layer can contain up to 30% amorphous and chlorine levels up to 3 at%.
  • the consisting of a hard metal, a cermet or a ceramic substrate body is subjected to a CVD coating at coating temperatures between 650 ° C and 900 ° C, wherein in the gas atmosphere titanium and aluminum chlorides and ammonia are introduced to produce a TiAlN layer.
  • a first between 2 .mu.m and 10 .mu.m, preferably 3 .mu.m to 7 .mu.m thick layer is applied in a conventional manner by means of the CVD method at least 2 microns, at most 10 microns thick Al 2 O 3 layer.

Description

Die Erfindung betrifft einen hartstoffbeschichteten Körper mit mehreren mittels CVD aufgetragenen Hartstoffschichten.The invention relates to a hard-coated body with a plurality of CVD applied hard material layers.

An Schneidwerkzeuge, die für die zerspanende Bearbeitung verwendet werden, werden hohe Anforderungen hinsichtlich der Standfestigkeit und der Belastbarkeit gestellt, insbesondere bei der Zerspanung harter oder zäher Materialien wie vergüteten bzw. gehärteten Stählen durch Drehen mit hohen Schnittgeschwindigkeiten. Der Schneidwerkstoff soll insbesondere abrasionsbeständig sein, was bereits frühzeitig dazu führte, dass Hartmetall- oder Cermetsubstratkörper mit Oberflächenbeschichtungen versehen worden sind, wobei zunächst Carbide, Nitride oder Carbonitride des Titans und später auch Aluminiumoxidschichten als Verschleißschutzschichten verwendet worden sind. Bekannt sind auch mehrlagige Verschleißschutzschichten aus unterschiedlichen Hartstoffen. Als verschleißmindernde Schichten sind beispielsweise Aluminiumoxidschichten bekannt, die auf einer oder mehreren Zwischenlagen wie beispielsweise Titancarbonitrid oder Titannitrid angeordnet sind.High demands are placed on cutting tools and tools used for machining operations, especially in the machining of hard or tough materials such as tempered or hardened steels by turning at high cutting speeds. In particular, the cutting material should be resistant to abrasion, which at an early stage has led to hard metal or cermet substrate bodies being provided with surface coatings, with carbides, nitrides or carbonitrides of titanium and later aluminum oxide layers being used as wear protection layers. Also known are multi-layer wear protection layers of different hard materials. As wear-reducing layers, for example, aluminum oxide layers are known, which are arranged on one or more intermediate layers such as titanium carbonitride or titanium nitride.

Aus der WO 03/085152 A2 ist die Verwendung einer Ti-Al-N-Schicht bekannt, die als monophasige Schicht mit Aluminiumgehalten bis 60% mittels PVD erzeugt werden kann. Bei höheren Aluminiumgehalten entsteht allerdings ein Gemisch aus kubischem und hexagonalem TiAlN und bei noch höheren Aluminiumanteilen nur noch die weichere und nicht verschleißfeste hexagonale Wurtzitstruktur.From the WO 03/085152 A2 the use of a Ti-Al-N layer is known, which can be produced as a monophase layer with aluminum contents up to 60% by means of PVD. At higher aluminum contents, however, a mixture of cubic and hexagonal TiAlN is formed, and with even higher proportions of aluminum only the softer and not wear-resistant hexagonal wurtzite structure is formed.

Es ist auch bekannt, dass mittels Plasma-CVD einphasige Ti1-xAlxN-Hartstoffschichten mit x = 0,9 herstellbar sind. Nachteilig sind jedoch hierbei die unzureichende Homogenität der Schichtzusammensetzung und der relativ hohe Chlorgehalt in der Schicht.It is also known that one-phase Ti 1-x Al x N hard-material layers with x = 0.9 can be produced by means of plasma CVD. However, the disadvantages here are the insufficient homogeneity of the layer composition and the relatively high chlorine content in the layer.

Soweit für die Herstellung von Ti1-xAlxN-Hartstoffschichten PVD- oder Plasma-CVD-Verfahren eingesetzt wurden, war deren Anwendung auf Temperaturen unter 700 °C beschränkt. Nachteilig ist, dass die Beschichtung komplizierter Bauteilgeometrien Schwierigkeiten bereitet. PVD ist ein gerichteter Prozess, bei dem komplexe Geometrien unregelmäßig beschichtet werden. Das Plasma-CVD erfordert eine hohe Plasmahomogenität, da die Plasmaleistungsdichte einen direkten Einfluss auf das Ti/Al-Atomverhältnis der Schicht hat. Die Herstellung einphasiger kubischer Ti1-xAlxN-Schichten mit hohem Aluminiumanteil ist mit den industriell eingesetzten PVD-Verfahren nicht möglich.Insofar as PVD or plasma CVD processes were used for the production of Ti 1-x Al x N hard-material layers, their application was based on temperatures limited below 700 ° C. The disadvantage is that the coating of complicated component geometries presents difficulties. PVD is a directed process in which complex geometries are coated irregularly. Plasma CVD requires high plasma homogeneity because the plasma power density has a direct impact on the Ti / Al atomic ratio of the layer. The production of single-phase cubic Ti 1-x Al x N layers with a high aluminum content is not possible with the industrially used PVD processes.

Auch eine TiAIN-Abscheidung mit einem konventionellen CVD-Verfahren bei Temperaturen über 1.000 °C ist nicht möglich, da das metastabile Ti1-xAlxN bei solch hohen Temperaturen in TiN und hexagonales AIN zerfällt.Also, a TiAIN deposition with a conventional CVD method at temperatures above 1000 ° C is not possible because the metastable Ti 1-x Al x N decomposes at such high temperatures in TiN and hexagonal AIN.

Schließlich ist bei dem in der US 6,238,739 B1 beschriebenen Verfahren, durch einen thermischen CVD-Prozess ohne Plasmaunterstützung Ti1-xAlxN-Schichten mit x zwischen 0,1 und 0,6 bei Temperaturen zwischen 550 °C und 650 °C herzustellen, eine Eingrenzung auf kleinere Aluminiumgehalte mit x ≤ 0,6 gegeben. Als Gasmischung werden in dem dort beschriebenen Prozess Aluminium- und Titanchloride sowie NH3 und H2 verwendet. Auch bei dieser Beschichtung sind hohe Chlorgehalte bis zu 12 At% in Kauf zu nehmen.Finally, in the case of US 6,238,739 B1 to produce Ti 1-x Al x N layers with x between 0.1 and 0.6 at temperatures between 550 ° C and 650 ° C by a thermal CVD process without plasma assisting, a limitation to smaller aluminum contents with x ≤ 0.6 given. As the gas mixture, aluminum and titanium chlorides as well as NH 3 and H 2 are used in the process described there. Also with this coating high chlorine contents up to 12 At% are to be accepted.

In der WO 2007/003648 A1 wird zur Verbesserung der Verschleißfestigkeit und der Oxidationsbeständigkeit vorgeschlagen, einen hartstoffbeschichteten Körper mit einem ein- oder mehrlagigen Schichtsystem mittels CVD herzustellen, das mindestens eine Ti1-xAlxN-Hartstoffschicht enthält, wozu der Körper in einem Reaktor bei Temperaturen im Bereich von 700 °C bis 900 °C mittels CVD ohne Plasmaanregung beschichtet wird und als Precursoren Titanhalogenide, Aluminiumhalogenide und reaktive Stickstoffverbindungen verwendet werden, die bei erhöhter Temperatur gemischt werden. Im Ergebnis wird ein Körper mit einer einphasigen Ti1-xAlxN-Hartstoffschicht in der kubischen NaCl-Struktur mit einem Stöchiometriekoeffizienten x > 0,75 bis x = 0,93 oder einer mehrphasige Schicht erhalten, deren Hauptphase aus Ti1-xAlxN mit kubischer NaCl-Struktur mit einem Stöchiometriekoeffizienten x > 0,75 bis x = 0,93 besteht, wobei als weitere Phase Ti1-xAlxN in Wurtzitstruktur und/oder TiNx in NaCl-Struktur enthalten sind. Der Chlorgehalt liegt im Bereich zwischen 0,05 bis 0,9 At%. Aus diesem Dokument ist auch bekannt, dass die Ti1-xAlxN-Hartstoffschicht oder -schichten bis zu 30 Massen% amorphe Schichtbestandteile enthalten können. Der Härtewert der erhaltenen Schichten liegt im Bereich 2.500 HV bis 3.800 HV.In the WO 2007/003648 A1 For example, in order to improve the wear resistance and the oxidation resistance, it is proposed to produce a hard-coated body with a single or multilayer coating system by CVD containing at least one Ti 1-x Al x N hard material layer, including the body in a reactor at temperatures in the range of 700 ° C to 900 ° C is coated by CVD without plasma excitation and are used as precursors titanium halides, aluminum halides and reactive nitrogen compounds, which are mixed at elevated temperature. As a result, a body having a single phase Ti 1-x Al x N hard material layer in the cubic NaCl structure having a stoichiometric coefficient x> 0.75 to x = 0.93 or a multi-phase layer whose main phase is Ti 1-x is obtained Al x N with cubic NaCl structure with a stoichiometric coefficient x> 0.75 to x = 0.93, wherein as a further phase Ti 1-x Al x N in wurtzite structure and / or TiN x in NaCl structure are included. The chlorine content is in the range between 0.05 to 0.9 At%. It is also known from this document that the Ti 1-x Al x N hard material layer or layers up to 30% by mass amorphous layer components may contain. The hardness value of the layers obtained is in the range of 2,500 HV to 3,800 HV.

Um die Haftung einer Ti1-xAlxN-Hartstoffschicht bei hoher Verschleißfestigkeit zu verbessern, wird in der nicht vorveröffentlichten DE 10 2007 000 512 zudem vorgeschlagen, dass das auf einen Substratkörper aufgetragene Schichtsystem aus einer auf den Körper aufgebrachten Anbindungsschicht aus Titannitrid, Titancarbonitrid oder Titancarbid besteht, worauf eine Phasengradientenschicht folgt und schließlich eine Außenlage aus einer ein- oder mehrphasigen Ti1-xAlxN-Hartstoffschicht. Die Phasengradientenschicht besteht an ihrer der Anbindungsschicht zugewandten Seite aus einem TiN/h-AIN-Phasengemisch und weist mit zunehmender Schichtdicke einen zunehmenden Phasenanteil von fcc-TiAIN mit einem Anteil von mehr als 50% und damit einhergehend simultaner Abnahme der Phasenanteile von TiN und h-AlN auf.In order to improve the adhesion of a Ti 1-x Al x N hard material layer with high wear resistance, is in the non-prepublished DE 10 2007 000 512 Furthermore, it is proposed that the layer system applied to a substrate body consists of a titanium nitride, titanium carbonitride or titanium carbide bonding layer applied to the body, followed by a phase gradient layer and finally an outer layer of a single- or multi-phase Ti 1-x Al x N hard-material layer. The phase gradient layer consists of a TiN / h-AlN phase mixture on its side facing the connection layer and, with increasing layer thickness, has an increasing phase fraction of fcc-TiAIN with a proportion of more than 50% and, concomitantly, a simultaneous decrease in the phase proportions of TiN and h- AlN on.

Neben der Abrasions- und Oxidationsbeständigkeit einer Schicht auf einem Hartmetall-, Cermet- oder Substratkörper ist für die Anwendung dieses Werkstoffes bei zerspanenden Bearbeitungen, insbesondere bei hohen Schnittgeschwindigkeiten, die thermische Beständigkeit der Beschichtung von großer Bedeutung. Im Bereich einer Schneidkante eines Schneideinsatzes entstehen beim Drehen von harten Werkstücken Temperaturen, die deutlich oberhalb von 1.000 °C liegen. Bei solchen Temperaturen wirken sich unterschiedliche Ausdehnungskoeffizienten, die für die Substrate zwischen den einzelnen Lagen bestehen, erheblich aus. Hierbei kommt es zur Ausbildung von Spannungen zwischen den einzelnen Lagen und, sofern durch Wärmeleitung die hohe Temperatur von der äußeren Schicht bis zum Substratkörper transportiert wird, im ungünstigsten Falle zu einem Ablösen der Beschichtung, womit der Schneideinsatz unbrauchbar wird.In addition to the abrasion and oxidation resistance of a layer on a hard metal, cermet or substrate body, the thermal resistance of the coating is of great importance for the application of this material in machining operations, in particular at high cutting speeds. In the area of a cutting edge of a cutting insert, when turning hard workpieces, temperatures are clearly above 1000 ° C. At such temperatures, different coefficients of expansion that exist for the substrates between the individual layers, significantly. This leads to the formation of stresses between the individual layers and, if the high temperature is transported by heat conduction from the outer layer to the substrate body, in the worst case to a detachment of the coating, making the cutting insert is unusable.

Es ist somit Aufgabe der vorliegenden Erfindung, einen hartstoffbeschichteten Körper zu schaffen, dessen Beschichtung durch Auswahl der einzelnen Schichten eine bessere thermische Isolationswirkung hinsichtlich des Wärmetransportes hat.It is therefore an object of the present invention to provide a hardstoffbeschichteten body whose coating has a better thermal insulation effect in terms of heat transfer by selecting the individual layers.

Diese Aufgabe wird durch einen hartstoffbeschichteten Körper nach Anspruch 1 gelöst. Der hartstoffbeschichtete Körper besitzt mehrere Schichten, wobei auf einer Ti1-xAlxN- und/oder Ti1-xAlxC- und/oder einer Ti1-xAlxCN-Schicht mit x = 0,65 bis 0,95 eine Al2O3-Schicht als Außenschicht angeordnet ist.This object is achieved by a hard-coated body according to claim 1. The hard-coated body has several layers, wherein on a Ti 1-x Al x N and / or Ti 1-x Al x C and / or a Ti 1-x Al x CN layer with x = 0.65 to 0.95 an Al 2 O 3 layer is arranged as an outer layer.

Die Verwendung einer Ti1-xAlxN-, Ti1-xAlxC- oder Ti1-xAlxCN-Schicht anstelle einer nach dem Stand der Technik allgemein verwendeten TiCN-Schicht hat den Vorteil, dass die Wärmeleitfähigkeit in der unterhalb der Al2O3-Schicht angeordneten Schicht um etwa 80% geringer ist, so dass sich die Ti1-xAlxN-, Ti1-xAlxC- oder Ti1-xAlxCN-Schicht als signifikant verbesserte thermische Isolation zum Substratkörper erweist. Die äußere Al2O3-Schicht ist auch oxidationsbeständiger und im Vergleich zu einer TiCN-Außenlage um ca. 50% härter, so dass sich eine höhere Verschleißbeständigkeit ergibt.The use of a Ti 1-x Al x N, Ti 1-x Al x C or Ti 1-x Al x CN layer instead of a TiCN layer commonly used in the prior art has the advantage that the thermal conductivity in the layer disposed below the Al 2 O 3 layer is about 80% smaller, so that the Ti 1-x Al x N, Ti 1-x Al x C or Ti 1-x Al x CN layer as significantly improved thermal isolation to the substrate body proves. The outer Al 2 O 3 layer is also more resistant to oxidation and harder by about 50% compared to a TiCN outer layer, resulting in a higher wear resistance.

Überraschenderweise ist darüber hinaus festgestellt worden, dass eine Ti1-xAlxN-, Ti1-xAlxC- oder Ti1-xAlxCN-Schicht als Zwischenlage im Vergleich zu einer TiN- oder TiCN-Zwischenlage keine Rissneigung besitzt, so dass sich das nach dem Stand der Technik nachteilig auswirkende typische Rissnetz nicht ausbildet. Insbesondere bei unterbrochenem Schnitt wirkt sich der verbesserte Rissbildungswiderstand standzeiterhöhend aus.Surprisingly, it has also been found that a Ti 1-x Al x N, Ti 1-x Al x C or Ti 1-x Al x CN layer as an intermediate layer in comparison to a TiN or TiCN interlayer no tendency to crack has, so that does not form the disadvantageous effect of the prior art typical crack network. In particular, with interrupted cut, the improved cracking resistance has a life-time increasing effect.

Die Ti1-xAlxCN-, Ti1-xAlxC- oder die Ti1-xAlxN-Schicht kann einphasig sein und eine kubische Struktur aufweisen, oder mehrphasig sein und neben einer kubischen Hauptphase eine weitere Phase in Wurtzitstruktur und/oder TiN aufweisen. Bis zu 30 Massen% können amorphe Schichtbestandteile enthalten sein. Der Chlorgehalt liegt zwischen 0,01 bis zu 3 At%.The Ti 1-x Al x CN, Ti 1-x Al x C or Ti 1-x Al x N layer may be single-phase and have a cubic structure, or be multi-phase, and another phase in addition to a cubic main phase Wurtzitstruktur and / or TiN have. Up to 30 mass% may contain amorphous layer constituents. The chlorine content is between 0.01 to 3 At%.

Nach einer Weiterbildung der Erfindung kann eine TiN- und/oder TiCN-Schicht als Anbindungsschicht an den Substratkörper, der aus einem Hartmetall, einem Cermet oder einer Keramik besteht, verwendet werden, so dass die Schichtfolge von innen nach außen TiN- oder TiCN-TiAlC(N)-Al2O3 lautet.According to a development of the invention, a TiN and / or TiCN layer can be used as a bonding layer to the substrate body, which consists of a hard metal, a cermet or a ceramic, so that the sequence of layers from inside to outside TiN or TiCN TiAlC (N) -Al 2 O 3 is.

Im Rahmen der vorliegenden Erfindung sind auch zwischen der Al2O3-Außenschicht und der Ti1-xAlxN-Schicht, Ti1-xAlxC-Schicht oder der Ti1-xAlxCN-Schicht TiCN-Schichten möglich.In the context of the present invention, TiCN layers are also present between the Al 2 O 3 outer layer and the Ti 1-x Al x N layer, Ti 1-x Al x C layer or the Ti 1-x Al x CN layer possible.

Vorzugsweise liegt der Aluminiumanteil als Metallanteil zwischen 70% und 90%. Die Schichtdicke einer Ti1-xAlxN-Schicht, Ti1-xAlxC-Schicht oder einer Ti1-xAlxCN-Schicht kann zwischen 2 µm bis 10 µm, vorzugsweise 3 µm bis 7 µm, variieren. Die vorgenannte Schicht kann auch Anteile an hexagonalem Aluminiumnitrid enthalten, maximal 25%.The aluminum content as metal content is preferably between 70% and 90%. The layer thickness of a Ti 1-x Al x N layer, Ti 1-x Al x C layer or a Ti 1-x Al x CN layer may be between 2 μm to 10 μm, preferably 3 μm to 7 μm, vary. The aforementioned layer may also contain proportions of hexagonal aluminum nitride, at most 25%.

Im Rahmen der vorliegenden Erfindung ist es auch möglich, anstelle einer einzigen Zwischenlage eine mehrlagige Schicht aus einer oder mehreren Doppellagen oder Dreifachlagen des Typs (Ti1-xAlxN, Ti1-xAlxC, Ti1-xAlxCN)n mit n = natürlicher Zahl anzuordnen. Die TiAlN/TiAlCN/TiAlC-Wechselschicht besitzt dann eine Gesamtdicke, die sich aus der Summe der Dicken jeder einzelnen Schicht ergibt, welche zwischen 1 nm bis 5 nm liegt. Vorzugsweise sollte die Gesamtdicke mindestens 1 µm bis 5 µm betragen. Im einfachsten Fall werden jeweils dünne, lediglich einige nm dicke Einzellagen aus Ti1-xAlxN oder Ti1-xAlxCN oder Ti1-xAlxC nacheinander bis zum Erreichen der gewünschten Gesamtdicke zwischen 1 µm und 5 µm aufgetragen. Es ist jedoch auch ein alternierendes Schichtsystem aus den vorgenannten Zusammensetzungen möglich, einschließlich solcher Schichten, die Lagen mit einem Gradientenverlauf besitzen, bei dem der C-Anteil nach außen sinkt oder steigt.In the context of the present invention it is also possible, instead of a single intermediate layer, to use a multilayered layer of one or more double layers or triple layers of the type (Ti 1-x Al x N, Ti 1-x Al x C, Ti 1-x Al x CN ) n with n = natural number. The TiAlN / TiAlCN / TiAlC alternating layer then has a total thickness resulting from the sum of the thicknesses of each individual layer, which is between 1 nm to 5 nm. Preferably, the total thickness should be at least 1 micron to 5 microns. In the simplest case thin, only a few nm thick individual layers of Ti 1-x Al x N or Ti 1-x Al x CN or Ti 1-x Al x C are successively applied to reach the desired total thickness between 1 micron and 5 microns , However, it is also possible to use an alternating layer system of the abovementioned compositions, including those layers which have layers with a gradient profile in which the C content decreases or increases to the outside.

Die TiAlN-, TiAIC- oder TiAICN-Schicht kann bis zu 30% amorphe Bestandteile und Chlorgehalte bis zu 3 At% beinhalten.The TiAlN, TiAIC or TiAICN layer can contain up to 30% amorphous and chlorine levels up to 3 at%.

Zur Herstellung wird der aus einem Hartmetall, einem Cermet oder einer Keramik bestehende Substratkörper einer CVD-Beschichtung bei Beschichtungstemperaturen zwischen 650 °C und 900 °C unterzogen, wobei in die Gasatmosphäre Titan- und Aluminiumchloride sowie Ammoniak zur Herstellung einer TiAlN-Schicht eingeleitet werden. Nach Herstellung einer ersten, zwischen 2 µm und 10 µm, vorzugsweise 3 µm bis 7 µm, dicken Schicht wird in konventioneller Weise mittels des CVD-Verfahrens eine mindestens 2 µm, maximal 10 µm dicke Al2O3-Schicht aufgetragen.For the production, the consisting of a hard metal, a cermet or a ceramic substrate body is subjected to a CVD coating at coating temperatures between 650 ° C and 900 ° C, wherein in the gas atmosphere titanium and aluminum chlorides and ammonia are introduced to produce a TiAlN layer. After producing a first, between 2 .mu.m and 10 .mu.m, preferably 3 .mu.m to 7 .mu.m thick layer is applied in a conventional manner by means of the CVD method at least 2 microns, at most 10 microns thick Al 2 O 3 layer.

Claims (9)

  1. Hard-coated body having a plurality of layers each applied by means of CVD to a substrate,
    characterized in that the substrate is a hard metal, a cermet or a ceramic on which an Al2O3 layer is deposited as an outer layer on a Ti1-xAlxN layer and/or Ti1-xAlxC layer and/or Ti1-xAlxCN layer with x = 0.65 to 0.95, the body being a cutting tool for interrupted cuts.
  2. Hard-coated body according to claim 1, characterized by a TiN and/or TiCN layer as a bonding layer to the substrate.
  3. Hard-coated body according to claim 1 or 2, characterized in that a TiCN layer is arranged between the Al2O3 outer layer and the Ti1-xAlxN layer, Ti1-xAlxC layer or Ti1-xAlxCN layer.
  4. Hard-coated body according to one of claims 1 to 3, characterized in that Ti1-xAlxN layer, Ti1-xAlxC layer or Ti1-xAlxCN layer is 0.7 ≤ x ≤ 0.9.
  5. Hard-coated body according to one of claims 1 to 4, characterized in that a multi-ply layer of one or a plurality of double layers or triple layers from the group (Ti1-xAlxN, Ti1-xAlxCN, Ti1-xAlxC)n is arranged beneath the Al2O3 layer.
  6. Hard-coated body according to one of claims 1 to 5, characterized in that the thickness of the outer layer is between 1 µm to 5 µm, the thickness of the Ti1-xAlxN layer, Ti1-xAlxC layer or Ti1-xAlxCN layer is 1 µm to 5 µm and the thickness of any additional bonding or intermediate layers is between 1 µm to 5 µm.
  7. Hard-coated body according to one of claims 1 to 6, characterized in that the Ti1-xAlxN layer, Ti1-xAlxC layer or Ti1-xAlxCN layer contains a maximum of 25 % of hexagonal AIN.
  8. Hard-coated body according to one of claims 1 to 7, characterized in that the Ti1-xAlxN layer, Ti1-xAlxC layer or Ti1-xAlxCN layer does not form a cracking network.
  9. Use of a hard-coated body according to one of claims 1 to 8 as a cutting tool for cutting with interrupted cutting.
EP15185878.4A 2008-03-12 2009-01-20 Body coated with hard material Revoked EP3031948B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL15185878T PL3031948T3 (en) 2008-03-12 2009-01-20 Body coated with hard material

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102008013965A DE102008013965A1 (en) 2008-03-12 2008-03-12 Hard material coated body
EP09718954.2A EP2252721B1 (en) 2008-03-12 2009-01-20 Body coated with hard material

Related Parent Applications (2)

Application Number Title Priority Date Filing Date
EP09718954.2A Division EP2252721B1 (en) 2008-03-12 2009-01-20 Body coated with hard material
EP09718954.2A Division-Into EP2252721B1 (en) 2008-03-12 2009-01-20 Body coated with hard material

Publications (2)

Publication Number Publication Date
EP3031948A1 EP3031948A1 (en) 2016-06-15
EP3031948B1 true EP3031948B1 (en) 2017-03-15

Family

ID=40586932

Family Applications (2)

Application Number Title Priority Date Filing Date
EP09718954.2A Active EP2252721B1 (en) 2008-03-12 2009-01-20 Body coated with hard material
EP15185878.4A Revoked EP3031948B1 (en) 2008-03-12 2009-01-20 Body coated with hard material

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP09718954.2A Active EP2252721B1 (en) 2008-03-12 2009-01-20 Body coated with hard material

Country Status (13)

Country Link
US (1) US8389134B2 (en)
EP (2) EP2252721B1 (en)
JP (1) JP5863241B2 (en)
KR (1) KR20100122918A (en)
CN (2) CN103834928B (en)
BR (1) BRPI0908924B1 (en)
CA (1) CA2717187C (en)
DE (1) DE102008013965A1 (en)
ES (2) ES2561597T3 (en)
MX (1) MX2010009890A (en)
PL (2) PL2252721T3 (en)
RU (1) RU2491368C2 (en)
WO (1) WO2009112115A1 (en)

Families Citing this family (51)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102009046667B4 (en) * 2009-11-12 2016-01-28 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Coated bodies of metal, hardmetal, cermet or ceramic, and methods of coating such bodies
AT510963B1 (en) 2011-03-18 2012-08-15 Boehlerit Gmbh & Co Kg COATED BODY AND METHOD FOR THE PRODUCTION THEREOF
AT510981B1 (en) * 2011-03-18 2012-08-15 Boehlerit Gmbh & Co Kg COATED BODY, USE THEREOF AND METHOD FOR THE PRODUCTION THEREOF
WO2013031915A1 (en) * 2011-08-30 2013-03-07 京セラ株式会社 Cutting tool
JP6024981B2 (en) 2012-03-09 2016-11-16 三菱マテリアル株式会社 A surface-coated cutting tool that exhibits excellent chipping resistance with a hard coating layer in high-speed intermittent cutting
JP5935479B2 (en) * 2012-04-20 2016-06-15 三菱マテリアル株式会社 Surface-coated cutting tool with excellent chipping resistance with a hard coating layer in high-speed milling and high-speed intermittent cutting
JP6044401B2 (en) * 2012-04-20 2016-12-14 三菱マテリアル株式会社 A surface-coated cutting tool that exhibits excellent chipping resistance with a hard coating layer in high-speed intermittent cutting
JP5939509B2 (en) * 2012-07-25 2016-06-22 三菱マテリアル株式会社 A surface-coated cutting tool that exhibits excellent chipping resistance with a hard coating layer in high-speed intermittent cutting
JP5939508B2 (en) * 2012-07-25 2016-06-22 三菱マテリアル株式会社 A surface-coated cutting tool that exhibits excellent chipping resistance with a hard coating layer in high-speed intermittent cutting
JP6090063B2 (en) * 2012-08-28 2017-03-08 三菱マテリアル株式会社 Surface coated cutting tool
JP6037113B2 (en) * 2012-11-13 2016-11-30 三菱マテリアル株式会社 A surface-coated cutting tool that exhibits excellent chipping resistance with a hard coating layer in high-speed intermittent cutting
JP6044336B2 (en) * 2012-12-27 2016-12-14 三菱マテリアル株式会社 Surface coated cutting tool with excellent chipping resistance due to hard coating layer
US9103036B2 (en) 2013-03-15 2015-08-11 Kennametal Inc. Hard coatings comprising cubic phase forming compositions
JP6268530B2 (en) * 2013-04-01 2018-01-31 三菱マテリアル株式会社 Surface coated cutting tool with excellent chipping resistance due to hard coating layer
JP6150109B2 (en) * 2013-04-18 2017-06-21 三菱マテリアル株式会社 Surface coated cutting tool with excellent chipping resistance due to hard coating layer
DE102013104254A1 (en) 2013-04-26 2014-10-30 Walter Ag Tool with CVD coating
US9896767B2 (en) 2013-08-16 2018-02-20 Kennametal Inc Low stress hard coatings and applications thereof
US9168664B2 (en) 2013-08-16 2015-10-27 Kennametal Inc. Low stress hard coatings and applications thereof
CA2922827C (en) * 2013-08-21 2017-01-31 Tungaloy Corporation Coated cutting tool
JP6391045B2 (en) * 2014-01-29 2018-09-19 三菱マテリアル株式会社 A surface-coated cutting tool that exhibits excellent chipping resistance with a hard coating layer in high-speed intermittent cutting
DE102014103220A1 (en) 2014-03-11 2015-09-17 Walter Ag TiAIN layers with lamellar structure
JP6402662B2 (en) * 2014-03-26 2018-10-10 三菱マテリアル株式会社 Surface-coated cutting tool and manufacturing method thereof
RU2695245C2 (en) * 2014-04-09 2019-07-22 Нуово Пиньоне СРЛ Method of turbo machine component protection against erosion under action of liquid drops, component and turbomachine
JP6548071B2 (en) * 2014-04-23 2019-07-24 三菱マテリアル株式会社 Surface coated cutting tool exhibiting excellent chipping resistance with hard coating layer
JP6548073B2 (en) 2014-05-28 2019-07-24 三菱マテリアル株式会社 Surface coated cutting tool exhibiting excellent chipping resistance with hard coating layer
JP5924507B2 (en) 2014-09-25 2016-05-25 三菱マテリアル株式会社 Surface coated cutting tool with excellent chipping resistance due to hard coating layer
EP3000913B1 (en) * 2014-09-26 2020-07-29 Walter Ag Coated cutting tool insert with MT-CVD TiCN on TiAI(C,N)
JP6620482B2 (en) * 2014-09-30 2019-12-18 三菱マテリアル株式会社 Surface coated cutting tool with excellent chipping resistance
JP6120229B2 (en) 2015-01-14 2017-04-26 住友電工ハードメタル株式会社 Hard coating, cutting tool, and manufacturing method of hard coating
JP6590255B2 (en) 2015-03-13 2019-10-16 三菱マテリアル株式会社 Surface coated cutting tool with excellent chipping resistance due to hard coating layer
US9994717B2 (en) * 2015-04-13 2018-06-12 Kennametal Inc. CVD-coated article and CVD process of making the same
WO2017038840A1 (en) * 2015-08-31 2017-03-09 三菱マテリアル株式会社 Surface-coated cutting tool having rigid coating layer exhibiting excellent chipping resistance
JP6726403B2 (en) 2015-08-31 2020-07-22 三菱マテリアル株式会社 Surface-coated cutting tool with excellent hard coating layer and chipping resistance
CN105195768A (en) * 2015-09-10 2015-12-30 苏州华冲精密机械有限公司 High-hardness thermal-insulation cutter
JP6931452B2 (en) 2015-10-30 2021-09-08 三菱マテリアル株式会社 Surface coating cutting tool with excellent wear resistance and chipping resistance for the hard coating layer
JP6931453B2 (en) 2015-10-30 2021-09-08 三菱マテリアル株式会社 Surface coating cutting tool with excellent chipping resistance due to the hard coating layer
DE102016108734B4 (en) * 2016-05-11 2023-09-07 Kennametal Inc. Coated body and method of making the body
EP3263738B1 (en) * 2016-07-01 2018-12-05 Walter Ag Cutting tool with textured alumina layer
JP6905807B2 (en) 2016-08-29 2021-07-21 三菱マテリアル株式会社 Surface coating cutting tool with excellent chipping resistance and peeling resistance with a hard coating layer
WO2018047735A1 (en) * 2016-09-06 2018-03-15 住友電工ハードメタル株式会社 Cutting tool and method for producing same
WO2018047733A1 (en) * 2016-09-06 2018-03-15 住友電工ハードメタル株式会社 Cutting tool and method for producing same
WO2018047734A1 (en) * 2016-09-06 2018-03-15 住友電工ハードメタル株式会社 Cutting tool and method of producing same
JP6781954B2 (en) * 2017-01-25 2020-11-11 三菱マテリアル株式会社 Surface coating cutting tool with excellent chipping resistance and peeling resistance with a hard coating layer
US11286570B2 (en) 2017-01-26 2022-03-29 Walter Ag Coated cutting tool
JP6796257B2 (en) * 2017-03-01 2020-12-09 三菱マテリアル株式会社 Surface coating cutting tool with excellent chipping resistance and peeling resistance with a hard coating layer
CN109112500B (en) * 2017-06-22 2022-01-28 肯纳金属公司 CVD composite refractory coating and application thereof
CN108479421B (en) * 2018-05-24 2020-08-28 萍乡市三盈科技有限公司 Manufacturing method of efficient inorganic membrane filter plate for water treatment
EP3848484A3 (en) 2020-01-10 2021-09-15 Sakari Ruppi Improved alumina layer deposited at low temperature
JP7329180B2 (en) 2020-02-03 2023-08-18 三菱マテリアル株式会社 surface coated cutting tools
JP7274107B2 (en) 2021-04-12 2023-05-16 株式会社タンガロイ coated cutting tools
JP7253153B2 (en) 2021-04-30 2023-04-06 株式会社タンガロイ coated cutting tools

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09125249A (en) 1995-11-07 1997-05-13 Hitachi Tool Eng Ltd Coated cemented carbide tool
DE19630791A1 (en) 1996-07-31 1998-02-05 Kennametal Hertel Ag Coated hard metal or cermet especially for cutter insert
JP2001341008A (en) 2000-06-02 2001-12-11 Hitachi Tool Engineering Ltd Titanium nitride-aluminum film coated tool and manufacturing method therefor
JP2002263911A (en) 2001-03-09 2002-09-17 Mitsubishi Materials Corp Surface-covered cemented carbide cutter having hard cover layer exhibiting excellent wear resistance in high- speed cutting operation
EP1470879A1 (en) 2002-01-21 2004-10-27 Mitsubishi Materials Kobe Tools Corporation Surface coated cutting tool member having hard coating layer exhibiting excellent abrasion resistance in high-speed cutting, and method for forming said hard coating layer on surface of cutting tool
WO2007003648A1 (en) 2005-07-04 2007-01-11 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Hard-coated body and method for production thereof
US20110003216A1 (en) 2007-08-02 2011-01-06 Canon Kabushiki Kaisha Fuel cell and fuel cell system

Family Cites Families (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4110006A1 (en) * 1991-03-27 1992-10-01 Krupp Widia Gmbh Composite body comprising alpha-alumina layer deposited by plasma CVD on a hard metal - where half-intensity width of the alumina X=ray diffraction lines is at least three times greater than normal
DE4209975A1 (en) * 1992-03-27 1993-09-30 Krupp Widia Gmbh Composite body and its use
SE502223C2 (en) * 1994-01-14 1995-09-18 Sandvik Ab Methods and articles when coating a cutting tool with an alumina layer
US5879823A (en) * 1995-12-12 1999-03-09 Kennametal Inc. Coated cutting tool
FR2745299B1 (en) 1996-02-27 1998-06-19 Centre Nat Rech Scient TI1-XALXN COATING FORMATION PROCESS
DE59709451D1 (en) 1996-09-03 2003-04-10 Unaxis Balzers Ag WEAR PROTECTION-COATED WORKPIECE
FR2767841B1 (en) * 1997-08-29 1999-10-01 Commissariat Energie Atomique PROCESS FOR THE PREPARATION BY CHEMICAL VAPOR DEPOSITION (CVD) OF A MULTI-LAYER COATING BASED ON Ti-Al-N
SE520802C2 (en) * 1997-11-06 2003-08-26 Sandvik Ab Cutting tool coated with alumina and process for its manufacture
SE517046C2 (en) * 1997-11-26 2002-04-09 Sandvik Ab Plasma-activated CVD method for coating fine-grained alumina cutting tools
EP0980917B1 (en) * 1998-07-29 2002-07-03 Toshiba Tungaloy Co., Ltd. Aluminium oxide-coated tool member
SE521284C2 (en) 1999-05-19 2003-10-21 Sandvik Ab Aluminum oxide coated cutting tool for metalworking
DE19962056A1 (en) * 1999-12-22 2001-07-12 Walter Ag Cutting tool with multi-layer, wear-resistant coating
DE10002861A1 (en) * 2000-01-24 2001-08-09 Walter Ag Cutting tool with carbonitride coating
US6572991B1 (en) * 2000-02-04 2003-06-03 Seco Tools Ab Deposition of γ-Al2O3 by means of CVD
JP2002126911A (en) * 2000-10-18 2002-05-08 Mitsubishi Materials Corp Cutting tool made of surface-covered cemented carbide excellent in surface lubricity against chip
JP3829322B2 (en) * 2001-09-03 2006-10-04 三菱マテリアル株式会社 Surface coated cemented carbide cutting tool with excellent adhesion and chipping resistance with wear resistant coating layer
AU2003227598A1 (en) 2002-04-11 2003-10-20 Cemecon Ag Coated bodies and a method for coating a body
AU2003254888A1 (en) * 2002-08-08 2004-02-25 Kabushiki Kaisha Kobe Seiko Sho PROCESS FOR PRODUCING ALUMINA COATING COMPOSED MAINLY OF Alpha-TYPE CRYSTAL STRUCTURE, ALUMINA COATING COMPOSED MAINLY OF Alpha-TYPE CRYSTAL STRUCTURE, LAMINATE COATING INCLUDING THE ALUMINA COATING, MEMBER CLAD WITH THE ALUMINA COATING OR LAMINATE COATING, PROCESS FOR PRODUCING THE MEMBER, AND PHYSICAL EVAPORATION APPARATU
JP4173762B2 (en) * 2003-04-04 2008-10-29 株式会社神戸製鋼所 Method for producing alumina film mainly composed of α-type crystal structure and method for producing laminated film-coated member
JP4398224B2 (en) * 2003-11-05 2010-01-13 住友電工ハードメタル株式会社 Wear resistant parts
JP2006028600A (en) * 2004-07-16 2006-02-02 Kobe Steel Ltd Stacked film having excellent wear resistance and heat resistance
US7972714B2 (en) * 2004-12-14 2011-07-05 Sumitomo Electric Hardmetal Corp. Coated cutting tool
US20070298280A1 (en) 2004-12-22 2007-12-27 Naoya Omori Surface-Coated Cutting Tool
US20090029132A1 (en) * 2005-11-17 2009-01-29 Boehlerit Gmbh & Co. Kg., Coated hard metal member
JP2008126334A (en) 2006-11-17 2008-06-05 Mitsubishi Heavy Ind Ltd Wear resistant film and tool having the same
DE102007000512B3 (en) 2007-10-16 2009-01-29 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Hard-coated body with a multi-layer system for tools and components such as drills, millers and indexable inserts, comprises a bonding layer applied on the body, a single- or multi-phase hard layer, and a phase gradient layer

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09125249A (en) 1995-11-07 1997-05-13 Hitachi Tool Eng Ltd Coated cemented carbide tool
DE19630791A1 (en) 1996-07-31 1998-02-05 Kennametal Hertel Ag Coated hard metal or cermet especially for cutter insert
JP2001341008A (en) 2000-06-02 2001-12-11 Hitachi Tool Engineering Ltd Titanium nitride-aluminum film coated tool and manufacturing method therefor
JP2002263911A (en) 2001-03-09 2002-09-17 Mitsubishi Materials Corp Surface-covered cemented carbide cutter having hard cover layer exhibiting excellent wear resistance in high- speed cutting operation
EP1470879A1 (en) 2002-01-21 2004-10-27 Mitsubishi Materials Kobe Tools Corporation Surface coated cutting tool member having hard coating layer exhibiting excellent abrasion resistance in high-speed cutting, and method for forming said hard coating layer on surface of cutting tool
WO2007003648A1 (en) 2005-07-04 2007-01-11 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Hard-coated body and method for production thereof
US20110003216A1 (en) 2007-08-02 2011-01-06 Canon Kabushiki Kaisha Fuel cell and fuel cell system

Non-Patent Citations (12)

* Cited by examiner, † Cited by third party
Title
"Improvement of energy resolution of EDS analysis of transmission", JOURNAL OF ELECTRON MICROSCOPY , FEMMS09 (THE TWELFTH FRONTIERS OF ELECTRON MICROSCOPY IN MATERIALS SCIENCE, 25 September 2009 (2009-09-25), Retrieved from the Internet <URL:http://www.femms2009.org>
A. ESCUDEIRO SANTANA ET AL.: "The role of hcp-AlN on hardness behavior of Ti"1"-"xAl"xN nanocomposite during annealing", THIN SOLID FILMS, vol. 469-470, 22 December 2004 (2004-12-22), pages 339 - 344, XP004663333
ANONYM: "EMAX-7000 brochure", HORIBA, pages 1 - 12
ANONYM: "Energiedispersive Rontgenspektroskopie", WIKIPEDIA, 28 February 2017 (2017-02-28), XP055441612, Retrieved from the Internet <URL:https://de.wikipedia.org/wiki/Energiedispersive_R%C3%B6ntgenspektroskopie>
ANONYM: "Fràsen", WIKIPEDIA, 24 October 2017 (2017-10-24), XP055441650, Retrieved from the Internet <URL:https://de.wikipedia.org/wiki/Fr5C3A4sen>
ANONYM: "Jahresbericht 2005", IKTS FRAUNHOFER INSTITUT KERAMISCHE TECHNOLOGIEN UND SYSTEME, 2005, pages 2 - 84, XP055441647
ANONYMOUS: "Kennametal Master Catalogue", 2001, pages 1 - 4, XP055441622
ANONYMOUS: "X-Ray Emission Lines", 16 May 2017 (2017-05-16), pages 1 - 2, XP055441618, Retrieved from the Internet <URL:http://www.med.harvard.edu/jpnm/physics/refs7xrayemis.html>
I. ENDLER ET AL.: "Aluminium-rich Ti1-xAlxN Coatings by CVD", EURO PM 2006-HARD MATERIALS, THIN AND THICK COATINGS, PROCEEDINGS, vol. 1, 1 October 2006 (2006-10-01), Ghent, Belgium, pages 219 - 224, XP008105516
I. ENDLER ET AL.: "Novel aluminium-rich Ti1-xAlxN coatings by LPCVD", SURFACE & COATINGS TECHNOLOGY 203 82008, vol. 203, no. 5-7, 25 December 2008 (2008-12-25), pages 530 - 533, XP002524222
I. ENDLER: "Al-rich ti1-xAlxN - A new CVD layer", FRAUNHOFER ADVANCER 3/2012, FRAUNHOFER ADVANCER ALLIANCE, DRESDEN, 1 March 2012 (2012-03-01), pages 1 - 4, XP055324865
M. KATHREIN ET AL.: "Wear Protection in Cutting Tool Applications by PACVD (Ti,AI)N and Al2O3 coatings", 15TH INTERNATIONAL PLANSEE SEMINAR, vol. 2, 2001, pages 726 - 738, XP055441626

Also Published As

Publication number Publication date
EP2252721A1 (en) 2010-11-24
CA2717187C (en) 2015-11-17
EP3031948A1 (en) 2016-06-15
CN103834928B (en) 2016-11-02
CN101970717A (en) 2011-02-09
JP5863241B2 (en) 2016-02-16
CN103834928A (en) 2014-06-04
RU2491368C2 (en) 2013-08-27
PL3031948T3 (en) 2017-07-31
RU2010141746A (en) 2012-04-20
DE102008013965A1 (en) 2009-09-17
ES2561597T3 (en) 2016-02-29
PL2252721T3 (en) 2016-02-29
BRPI0908924A2 (en) 2015-08-18
CA2717187A1 (en) 2009-09-17
JP2011516722A (en) 2011-05-26
US8389134B2 (en) 2013-03-05
ES2628524T3 (en) 2017-08-03
BRPI0908924B1 (en) 2024-01-23
WO2009112115A1 (en) 2009-09-17
MX2010009890A (en) 2010-09-30
EP2252721B1 (en) 2015-11-04
KR20100122918A (en) 2010-11-23
US20100323176A1 (en) 2010-12-23

Similar Documents

Publication Publication Date Title
EP3031948B1 (en) Body coated with hard material
EP2250299B1 (en) Body coated with hard material
DE112011101826B4 (en) Multilayer nitride hard coatings, hard coated article and method of making same
EP1902155B1 (en) Hard-coated body and method for production thereof
EP2601330B1 (en) Cutting tool comprising multilayer coating
DE60011494T2 (en) Coated milling insert
DE69527124T3 (en) Hard composite material for tools
DE112011101379T5 (en) Coating for cutting tools
EP2132358B1 (en) Multilayer cvd coating
EP1726687A2 (en) Coated tool
DE102016108734B4 (en) Coated body and method of making the body
DE10222347C2 (en) TiBN coating for a cutting insert or a cutting tool
DE112013002291T5 (en) Hard coating for a cutting tool
WO2009112117A1 (en) Body coated with hard material
EP1549781B1 (en) Composite material
WO2009144119A1 (en) Tool having a metal oxide coating
DE112013002302B4 (en) Hard coating for a cutting tool
DE102015115859A1 (en) Multilayer structured coatings for cutting tools
DE10360482B4 (en) Hard coating with excellent adhesion
EP2486164B1 (en) Cutting tool for machining of metallic materials
DE19815677A1 (en) Coated hard metal, cermet, steel, ceramic or metal alloy composite body e.g. a cutting tool such as a throwaway drill bit or cutter tip
DE112019005024T5 (en) Hard coating for cutting tool
EP2686463A1 (en) Coated body, use thereof, and method for production of same
EP1620578B1 (en) Tool and method for the chemical vapor deposition of a two-phase layer on a substrate member

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20150918

AC Divisional application: reference to earlier application

Ref document number: 2252721

Country of ref document: EP

Kind code of ref document: P

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK TR

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

RIC1 Information provided on ipc code assigned before grant

Ipc: C23C 28/04 20060101ALI20161121BHEP

Ipc: C23C 30/00 20060101ALI20161121BHEP

Ipc: C23C 16/36 20060101ALI20161121BHEP

Ipc: C23C 16/34 20060101ALI20161121BHEP

Ipc: C23C 16/32 20060101AFI20161121BHEP

Ipc: C23C 16/40 20060101ALI20161121BHEP

INTG Intention to grant announced

Effective date: 20161205

RIN1 Information on inventor provided before grant (corrected)

Inventor name: SOTTKE, VOLKMAR

Inventor name: WESTPHAL, HARTMUT

Inventor name: VAN DEN BERG, HENDRIKUS

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AC Divisional application: reference to earlier application

Ref document number: 2252721

Country of ref document: EP

Kind code of ref document: P

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: BUGNION S.A., CH

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 875661

Country of ref document: AT

Kind code of ref document: T

Effective date: 20170415

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 502009013770

Country of ref document: DE

REG Reference to a national code

Ref country code: SE

Ref legal event code: TRGR

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20170315

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170315

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170315

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170615

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170315

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170616

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2628524

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20170803

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170615

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170315

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170315

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170315

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170315

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170315

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170715

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170717

REG Reference to a national code

Ref country code: DE

Ref legal event code: R026

Ref document number: 502009013770

Country of ref document: DE

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PLAX Notice of opposition and request to file observation + time limit sent

Free format text: ORIGINAL CODE: EPIDOSNOBS2

26 Opposition filed

Opponent name: MITSUBISHI MATERIALS CORPORATION

Effective date: 20171213

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 10

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170315

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170315

PLBB Reply of patent proprietor to notice(s) of opposition received

Free format text: ORIGINAL CODE: EPIDOSNOBS3

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170315

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180120

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20180131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180120

RDAF Communication despatched that patent is revoked

Free format text: ORIGINAL CODE: EPIDOSNREV1

PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO

R26 Opposition filed (corrected)

Opponent name: MITSUBISHI MATERIALS CORPORATION

Effective date: 20171213

APBM Appeal reference recorded

Free format text: ORIGINAL CODE: EPIDOSNREFNO

APBP Date of receipt of notice of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNNOA2O

APAH Appeal reference modified

Free format text: ORIGINAL CODE: EPIDOSCREFNO

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170315

APBQ Date of receipt of statement of grounds of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNNOA3O

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20090120

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170315

Ref country code: MK

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170315

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20220127

Year of fee payment: 14

Ref country code: DE

Payment date: 20220127

Year of fee payment: 14

Ref country code: CH

Payment date: 20220202

Year of fee payment: 14

Ref country code: AT

Payment date: 20220103

Year of fee payment: 14

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: TR

Payment date: 20220112

Year of fee payment: 14

Ref country code: SE

Payment date: 20220127

Year of fee payment: 14

Ref country code: PL

Payment date: 20220111

Year of fee payment: 14

Ref country code: IT

Payment date: 20220119

Year of fee payment: 14

Ref country code: FR

Payment date: 20220125

Year of fee payment: 14

Ref country code: ES

Payment date: 20220201

Year of fee payment: 14

Ref country code: CZ

Payment date: 20220107

Year of fee payment: 14

APBU Appeal procedure closed

Free format text: ORIGINAL CODE: EPIDOSNNOA9O

REG Reference to a national code

Ref country code: DE

Ref legal event code: R103

Ref document number: 502009013770

Country of ref document: DE

Ref country code: DE

Ref legal event code: R064

Ref document number: 502009013770

Country of ref document: DE

RDAG Patent revoked

Free format text: ORIGINAL CODE: 0009271

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: PATENT REVOKED

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

27W Patent revoked

Effective date: 20221004

GBPR Gb: patent revoked under art. 102 of the ep convention designating the uk as contracting state

Effective date: 20221004

REG Reference to a national code

Ref country code: AT

Ref legal event code: MA03

Ref document number: 875661

Country of ref document: AT

Kind code of ref document: T

Effective date: 20221004

REG Reference to a national code

Ref country code: SE

Ref legal event code: ECNC