Coated cemented carbide bodies

Abstract

A process for increasing the resistance to wear of the surface of hard metal parts subject to wear, such as a cutting blade of metal cutting tools, and the product which results from the process, which includes coating the surface of the hard metal, for example, cemented carbide articles with a first layer comprised of one or more layers of a metallic carbide or nitride in a total thickness ranging from 0.01 to 10 μm, a second layer comprised of one or more layers of a refractory oxide, such as an oxide of aluminum, zirconium, silicon, calcium, magnesium, titanium, and hafnium, and stabilized zirconium oxide in a total thickness ranging from 0.5 to 10 μm, and depositing over the refractory oxide coating a third layer comprised of one or more layers of a nitride, carbonitride, oxynitride, oxycarbide or oxycarbonitride .[.and boride.]. of such metals as titanium, zirconium, hafnium, aluminum and silicon in a total thickness ranging from 1 to 10 μm. The process may include transitional layers to optimize the adherence of the various layers.

What is claimed as new is as follows: .[.1. A coated article for cutting tool and wear resistant applications which comprises a hard metal substrate and an abrasion and cratering resistant multiple layer coating on at least a portion of said substrate, said coating comprising: 
     
        layer..]. .[.3.  A coated article for cutting tool and wear resistant applications as defined in claim 1 in which a transition layer is formed between said first and second layers by providing an oxide on said first layer before applying said second layer..]. .[.4. A coated article for cutting tool and wear resistant applications as defined in claim 1 in which an amount of binder metal selected from iron, nickel and cobalt is provided in first layer adjacent the said substrate..]. .[.5. A coated article for cutting tool and wear resistant applications as defined in claim 1 in which the overall thickness of said three layers on said substrate is in a range from 1 to 30 μm..]. .[.6. A coated article for cutting tool and wear resistant applications as defined in claim 1 in which said first layer has a thickness in the range of 0.01 to 10 μm..]. .[.7. A coated article for cutting tool and wear resistant applications as defined in claim 1 in which said second layer has a thickness in the range of 0.5 to 10 μm..]. .[.8. A coated article for cutting tool and wear resistant applications as defined in claim 1 in which said third layer has a thickness in the range of 0.5 to 10 μm..]. .[.9. A coated article for cutting tool and wear resistant applications as defined in claim 1 in which said first layer comprises a composite layer of two or more layers selected from a carbide, nitride and carbonitride of metals selected from Groups IVB and VB of the Periodic Table of Elements and a carbide of metals selected from Group VIB of the Periodic Table of Elements..]. .[.10. A coated article for cutting tool and wear resistant applications as defined in claim 1 in which said refractory oxide of said second layer comprises a composite layer of two or more layers selected from an oxide of aluminum, zirconium, silicon, calcium, magnesium, titanium and hafnium, and stabilized zirconium oxide..]. .[.11. A coated article for cutting tool and wear resistant applications as defined in claim 1 in which said third layer comprises a layer selected from a nitride, carbonitride, oxynitride, and oxycarbonitride of metals selected from Group IVB of the Periodic Table of Elements, and aluminum and silicon..]. .[.12. A coated article for cutting tool and wear resistant applications as defined in claim 1 in which said third and final layer comprises a composite layer of two or more layers selected from a nitride, carbonitride, oxynitride, and oxycarbonitride of metals selected from Group IVB of the Periodic Table of Elements, and aluminum and silicon..]. .[.13. A coated article for cutting tool and wear resistant applications as defined in claim 11 in which, in the selected carbonitride, the carbon-to-nitrogen ratio is controlled to provide a nitrogen-rich carbonitride..]. .[.14. A coated article for cutting tool and wear resistant applications as defined in claim 11 in which, in the selected carbonitride, the carbon-to-nitrogen ratio is controlled to provide a carbon-rich carbonitride..]. .[.15. A coated article for cutting tool and wear resistant applications as defined in claim 1 in which the third, and final layer comprises a composite coating on said second layer, said composite coating comprising a layer of selected metal carbide overlying the second layer, a layer of selected metal carbonitride overlying the metal carbide, and a layer of a selected metal nitride overlying the metal carbonitride..]. .[.16. A coated article for cutting tool and wear resistant applications as defined in claim c.o.c. 1 in which the third layer comprises a composite coating on said second layer, said composite coating including a layer of titanium carbide, a transition layer containing titanium carbonitrides overlying said layer of titanium carbide, and a layer of titanium nitride overlying said transition layer..]. .[.17. A coated article for cutting tool and wear resistant applications as defined in claim 1 in which said third and final layer deposited on said second refractory oxide comprises a composite coating in transition from basic depositions high in concentration of the chemical elements constituting the second layer and low in concentration of the chemical elements of the third layer and progressing to increasing concentration of the chemical elements of the third layer and decreasing chemical elements of the second layer..]. .[.18. A coated article for cutting tool and wear resistant applications as defined in claim 11 in which said carbonitride of said third layer has a carbon content which is highest adjacent said second layer and varies in the thickness of said third layer to progressively lower carbon content and higher nitrogen content until the composition of the outermost stratum of said third layer has the highest nitrogen content in said carbonitride layer..]. .[.19. A coated article for cutting tool and wear resistant applications as defined in claim 1 in which said third and final layer deposited on said layer of refractory oxide comprises a composite coating in transition from basic depositions high in oxygen content in the compounds deposited and low in nitrogen content in the compounds formed adjacent the second layer and progressively decreasing in oxygen content and increasing in nitrogen content into the third layer..]. .[.20. A coated article for cutting tool and wear resistant applications as defined in claim 19 in which the refractory oxide of said layer is aluminum oxide and said third layer progresses in chemical composition from aluminum oxide of the second layer 
     
     
        to aluminum nitride..]. .[.21.  A coated article for cutting tool and wear resistant applications as defined in claim 1 in which the third layer is a composite layer comprised of multiple layers selected from two or more nitride compounds of metals in Group IVB of the Periodic Table of Elements, and of aluminum and of silicon..]. .[.22. A coated article for cutting tool and wear resistant applications which comprises a substrate and a coating on at least a portion of said substrate, said coating comprising: (a) a first layer selected from a carbide, nitride, and carbonitride of metals selected from Groups IVB and VB and of a carbide of metals selected from Group VIB of the Periodic Table of Elements,   (b) a second layer selected from an oxide of aluminum, zirconium, silicon, calcium, magnesium, titanium, and hafnium, and stabilized zirconium oxide, and   (c) a third and final layer selected from a nitride, carbonitride, oxynitride, and oxycarbonitride of metals selected from Group IVB of the Periodic Table of Elements, and of aluminum, and of silicon..]. .[.23. A coated article for cutting tool and wear resistant applications which comprises a substrate and a coating on at least a portion of said substrate, said coating comprising:   (a) a first layer comprising one or more layers selected from a carbide, nitride, and carbonitride of metals selected from Groups IVB and VB and of a carbide of metals selected from Group VIB of the Periodic Table of Elements,   (b) a second layer comprising one or more layers selected from an oxide of aluminum, zirconium, silicon, calcium, magnesium, titanium, and hafnium, and stabilized zirconium oxide, and   (c) a third and final layer comprising more than one layer selected from a nitride, carbonitride, oxynitride, and oxycarbonitride of metals selected from Group IVB of the Periodic Table of Elements, and of aluminum, and of   
     
     
        silicon..]. .Iadd.24.  A coated article for cutting tool and wear resistant applications which comprises a hard metal substrate and an abrasion and cratering resistant multiple layer coating on at least a portion of said substrate in which said coating includes: (a) a first layer selected from a carbide, nitride or carbonitride of metals selected from Groups IVB and VB and a carbide of metals selected from Group VIB of the Periodic Table of Elements,   (b) a second layer in the form of a refractory oxide selected from an oxide of aluminum, zirconium, silicon, calcium, magnesium, titanium and hafnium and stabilized zirconium oxide, and   (c) a third and final layer of nitride compounds of metals selected from Group IVB of the Periodic Table and aluminum and silicon, that improvement which comprises providing a transition layer between the second and third layers, the chemical composition of said transition layer varying from the composition of said second layer to the composition of said third layer.   
     
     
        .Iaddend. .Iadd.25.  A coated article for cutting tool and wear resistant applications which comprises a hard metal substrate and an abrasion and cratering resistant multiple layer coating on at least a portion of said substrate in which said coating includes: (a) a first layer selected from a carbide, nitride or carbonitride of metals selected from Groups IVB and VB and a carbide of metals selected from Group VIB of the Periodic Table of Elements,   (b) a second layer in the form of a refractory oxide selected from an oxide of aluminum, zirconium, silicon, calcium, magnesium, titanium and hafnium and stabilized zirconium oxide, and   (c) a third and final layer of nitride compounds of metals selected from Group IVB of the Periodic Table and aluminum and silicon, that improvement in which said first layer comprises a composite layer of two or more layers selected from a carbide, nitride and carbonitride of metals selected from Groups IVB and VB of the Periodic Table of Elements, and a carbide of metals selected from Group VIB of the Periodic Table of   
     
     
        Elements. .Iaddend. .Iadd.26.  A coated article for cutting tool and wear resistant applications which comprises a hard metal substrate and an abrasion and cratering resistant multiple layer coating on at least a portion of said substrate in which said coating includes: (a) a first layer selected from a carbide, nitride or carbonitride of metals selected from Groups IVB and VB and a carbide of metals selected from Group VIB of the Periodic Table of Elements,   (b) a second layer in the form of a refractory oxide selected from an oxide of aluminum, zirconium, silicon, calcium, magnesium, titanium and hafnium and stabilized zirconium oxide, and   (c) a third and final layer of nitride compounds of metals selected from Group IVB of the Periodic Table and aluminum and silicon, that improvement in which said third layer comprises a layer selected from a carbonitride, oxynitride and oxycarbonitride of metals selected from Group IVB of the Periodic Table of Elements, and a nitride and oxynitride of aluminum and silicon. .Iaddend. .Iadd.27. A coated article for cutting tool and wear resistant applications as defined in claim 26 in which, in a selected carbonitride, the carbon-to-nitrogen ratio is controlled to provide a nitrogen-rich carbonitride. .Iaddend. .Iadd.28. A coated article for cutting tool and wear resistant applications as defined in claim 26 in which, in a selected carbonitride, the carbon-to-nitrogen ratio is   
     
     
        controlled to provide a carbon-rich carbonitride. .Iaddend. .Iadd.29.  A coated article for cutting tool and wear resistant applications which comprises a hard metal substrate and an abrasion and cratering resistant multiple layer coating on at least a portion of said substrate in which said coating includes: (a) a first layer selected from a carbide, nitride or carbonitride of metals selected from Groups IVB and VB and a carbide of metals selected from Group VIB of the Periodic Table of Elements,   (b) a second layer in the form of a refractory oxide selected from an oxide of aluminum, zirconium, silicon, calcium, magnesium, titanium and hafnium and stabilized zirconium oxide, and   (c) a third and final layer of nitride compounds of metals selected from Group IVB of the Periodic Table and aluminum and silicon, that improvement in which the third layer comprises a composite coating on said second layer, said composite coating comprising a layer of selected metal carbide overlying the second layer, a layer of selected metal carbonitride overlying the metal carbide, and a layer of a selected metal nitride   
     
     
        overlying the metal carbonitride. .Iaddend. .Iadd.30.  A coated article for cutting tool and wear resistant applications which comprises a hard metal substrate and an abrasion and cratering resistant multiple layer coating on at least a portion of said substrate in which said coating includes: (a) a first layer selected from a carbide, nitride or carbonitride of metals selected from Groups IVB and VB and a carbide of metals selected from Group VIB of the Periodic Table of Elements,   (b) a second layer in the form of a refractory oxide selected from an oxide of aluminum, zirconium, silicon, calcium, magnesium, titanium and hafnium and stabilized zirconium oxide, and   (c) a third and final layer of nitride compounds of metals selected from Group IVB of the Periodic Table and aluminum and silicon, that improvement in which the third layer comprises a composite coating on said second layer, said composite coating including a layer of titanium carbide, a transition layer containing titanium carbonitrides overlying said layer of titanium carbide, and a layer of titanium nitride overlying said transition layer. .Iaddend. .Iadd.31. A coated article for cutting tool and wear resistant applications which comprises a hard metal substrate and an abrasion and cratering resistant multiple layer coating on at least a portion of said substrate in which said coating includes:   (a) a first layer selected from a carbide, nitride or carbonitride of metals selected from Groups IVB and VB and a carbide of metals selected from Group VIB of the Periodic Table of Elements,   (b) a second layer in the form of a refractory oxide selected from an oxide of aluminum, zirconium, silicon, calcium, magnesium, titanium and hafnium and stabilized zirconium oxide, and   (c) a third and final layer of nitride compounds of metals selected from Group IVB of the Periodic Table and aluminum and silicon, that improvement in which said third layer deposited on said second refractory oxide comprises a composite coating in transition from basic depositions high in concentration of the chemical elements constituting the second layer and low in concentration of the chemical elements of the third layer and progressing to increasing concentration of the chemical elements of the third layer and decreasing chemical elements of the second layer.   
     
     
        .Iaddend. .Iadd.32.  A coated article for cutting tool and wear resistant applications as defined in claim 26 in which a carbonitride of said third layer has a carbon content which is highest adjacent said second layer and varies in the thickness of said third layer to progressively lower carbon content and higher nitrogen content until the composition of the outermost stratum of said third layer has the highest nitrogen content in said 
     
     
        carbonitride layer. .Iaddend. .Iadd.33.  A coated article for cutting tool and wear resistant applications which comprises a hard metal substrate and an abrasion and cratering resistant multiple layer coating on at least a portion of said substrate in which said coating includes: (a) a first layer selected from a carbide, nitride or carbonitride of metals selected from Groups IVB and VB and a carbide of metals selected from Group VIB of the Periodic Table of Elements,   (b) a second layer in the form of a refractory oxide selected from an oxide of aluminum, zirconium, silicon, calcium, magnesium, titanium and hafnium and stabilized zirconium oxide, and   (c) a third and final layer of nitride compounds of metals selected from Group IVB of the Periodic Table and aluminum and silicon, that improvement in which said third layer deposited on said layer of refractory oxide comprises a composite coating in transition from basic depositions high in oxygen content in the compound deposited and lower in nitrogen content in the compounds formed adjacent the second layer and progressively decreasing in oxygen content and increasing in nitrogen content into the third layer. .Iaddend. .Iadd.34. A coated article for cutting tool and wear resistant applications as defined in claim 33 in which the refractory oxide of said layer is aluminum oxide and said third layer progresses in chemical composition from aluminum oxide of the second layer to aluminum   
     
     
        nitride. .Iaddend. .Iadd.35.  A coated article for cutting tool and wear resistant applications which comprises a hard metal substrate and an abrasion and cratering resistant multiple layer coating on at least a portion of said substrate in which said coating includes: (a) a first layer selected from a carbide, nitride or carbonitride of metals selected from Groups IVB and VB and a carbide of metals selected from Group VIB of the Periodic Table of Elements,   (b) a second layer in the form of a refractory oxide selected from an oxide of aluminum, zirconium, silicon, calcium, magnesium, titanium and hafnium and stabilized zirconium oxide, and   (c) a third and final layer of nitride compounds of metals selected from Group IVB of the Periodic Table and aluminum and silicon, that improvement which comprises a transition layer between the second and third layers selected from aluminum oxynitride, aluminum nitride, titanium carbide, titanium oxide, titanium oxycarbide, and titanium oxycarbonitride which phase from aluminum and oxygen rich at the initiation of the transition layer to titanium and nitrogen rich at the end of the transition.   
     
     
        .Iaddend. .Iadd.36.  A coated article for cutting tool and wear resistant applications which comprises a hard metal substrate and an abrasion and cratering resistant multiple layer coating on at least a portion of said substrate in which said coating includes: (a) a first layer selected from a carbide, nitride or carbonitride of metals selected from Groups IVB and VB and a carbide of metals selected from Group VIB of the Periodic Table of Elements,   (b) a second layer in the form of a refractory oxide selected from an oxide of aluminum, zirconium, silicon, calcium, magnesium, titanium and hafnium and stabilized zirconium oxide, and   (c) a third and final layer of nitride compounds of metals selected from Group IVB of the Periodic Table and aluminum and silicon, that improvement in which the second coat is aluminum oxide followed by a transition layer including aluminum oxynitride, the overall thickness of the layers being 8.7 to 14 μm, the thickness of the aluminum nitride including the   
     
     
        transition layer being 2.0 to 7.3 μm. .Iaddend. .Iadd.37.  A coated article as defined in claims 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34 or 35, in which the thickness of the second layer is 3 to 10 μm and the ratio of the thickness of the second layer to said first layer is greater than 0.5. .Iaddend. .Iadd.38. A coated article as defined in claims 24, 25, 26, 27 to 34 or 35 in which said second layer has a thickness of about 3.3 μm and said first layer has a thickness of about 5.3 μm..Iaddend. .Iadd.39. A coated article as defined in claims 24, 25, 26, 27 to 34 or 35 in which said third layer has a thickness of 2 to 10 μm to completely cover surface roughness and provide a uniform and smooth surface. .Iaddend.