USRE44870E1 - Aluminum oxide coated cutting tool and method of manufacturing thereof - Google Patents

Aluminum oxide coated cutting tool and method of manufacturing thereof Download PDF

Info

Publication number
USRE44870E1
USRE44870E1 US12/222,440 US22244008A USRE44870E US RE44870 E1 USRE44870 E1 US RE44870E1 US 22244008 A US22244008 A US 22244008A US RE44870 E USRE44870 E US RE44870E
Authority
US
United States
Prior art keywords
hkl
layer
alumina
grain size
alumina layer
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 - Lifetime
Application number
US12/222,440
Inventor
Bjorn Ljungberg
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.)
Sandvik Intellectual Property AB
Original Assignee
Sandvik Intellectual Property AB
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=20392562&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=USRE44870(E1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Sandvik Intellectual Property AB filed Critical Sandvik Intellectual Property AB
Priority to US12/222,440 priority Critical patent/USRE44870E1/en
Application granted granted Critical
Publication of USRE44870E1 publication Critical patent/USRE44870E1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

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
    • 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
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/02Pretreatment of the material to be coated
    • C23C16/0272Deposition of sub-layers, e.g. to promote the adhesion of the main coating
    • 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
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40Oxides
    • C23C16/403Oxides of aluminium, magnesium or beryllium
    • 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
    • Y10T407/00Cutters, for shaping
    • Y10T407/27Cutters, for shaping comprising tool of specific chemical composition

Definitions

  • the invention relates to a coated cutting tool for chip-forming machining, a method of making the tool and a method of machining metal with the tool.
  • Chemical Vapour Deposition (CVD) of alumina on cutting tools has been an industrial practice for more than 15 years.
  • the wear properties of Al 2 O 3 as well as of other refractory materials have been discussed extensively in the literature.
  • the CVD-technique has also been used to produce coatings of other metal oxides, carbides and nitrides, the metal being selected from transition metals of the IVB, VB and VIB groups of the Periodic Table. Many of these compounds have found practical applications as wear resistant or protective coatings, but few have received as much attention as TiC, TiN and Al 2 O 3 .
  • Cemented carbide cutting tools coated with various types of Al 2 O 3 -coatings e.g., pure ⁇ -Al 2 O 3 , mixtures of ⁇ - and ⁇ -Al 2 O 3 and very coarse-grained ⁇ -Al 2 O 3 have been commercially available for many years.
  • Al 2 O 3 crystallizes in several different phases: ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , etc.
  • the two most frequently occurring phases in CVD of wear resistant Al 2 O 3 -coatings are the thermodynamically stable, hexagonal ⁇ -phase and the metastable ⁇ -phase.
  • the ⁇ -phase is fine-grained with a grain size in the range 0.5-2.0 ⁇ m and often exhibits a columnar coating morphology.
  • ⁇ -Al 2 O 3 coatings are free from crystallographic defects and free from micropores or voids.
  • the ⁇ -Al 2 O 3 grains are usually coarser with a grain size of 1-6 ⁇ m depending upon the deposition conditions. Porosity and crystallographic defects are in this case more common.
  • both ⁇ - and ⁇ -phase are present in a CVD alumina coating deposited onto a cutting tool.
  • Al 2 O 3 is always applied on TiC coated carbide or ceramic substrates (see, e.g., U.S. Pat. No. 3,837,896, now U.S. Reissue Pat. No. 29,420) and therefore the interfacial chemical reactions between the TiC-surface and the alumina coating are of particular importance.
  • the TiC layer should also be understood to include layers having the formula TiC x N y O z in which the carbon in TiC is completely or partly substituted by oxygen and/or nitrogen.
  • U.S. Pat. No. 4,619,866 to Smith describes a method for producing fast growing Al 2 O 3 layers by utilizing a hydrolysis reaction of a metal halide under the influence of a dopant e.g., hydrogen sulphide (H 2 S) in the concentration range 0.01-0.2% at a CVD deposition temperature of 1000-1050° C.
  • a dopant e.g., hydrogen sulphide (H 2 S) in the concentration range 0.01-0.2% at a CVD deposition temperature of 1000-1050° C.
  • H 2 S hydrogen sulphide
  • the resulting coating consists of a mixture of the smaller ⁇ -grains and the larger ⁇ -grains.
  • the process yields coatings with an even layer thickness distribution around the coated body.
  • Commonly owned Swedish Patent Application No. 9304283-6 discloses a body with a coating comprising one or more refractory layers of which at least one layer is a layer of ⁇ -Al 2 O 3 textured in the (110) direction.
  • the alumina layer is essentially free of cooling cracks and comprises platelike grains with a length of 2-8 ⁇ m and a length/width-ratio of 1-10.
  • the alumina layer consists of single phase ⁇ -structure textured in the (104)-direction with a texture coefficient larger than 1.5, the texture coefficient being defined as:
  • TC ⁇ ( hkl ) I ⁇ ( hkl ) I o ⁇ ( hkl ) ⁇ ⁇ 1 n ⁇ ⁇ ⁇ ⁇ ⁇ I ⁇ ( hkl ) I o ⁇ ( hkl ) ⁇ - 1
  • I(hkl) measured intensity of the (hkl) reflection
  • I o (hkl) standard intensity of the ASTM standard powder pattern diffraction data
  • n number of reflections used in the calculation and (hkl) reflections used are: (012), (104), (110), (113), (024), (116).
  • the texture coefficient can be greater than 2.5, preferably greater than 3.0.
  • the alumina layer is preferably an exposed outermost layer. However, other layers can be present such as in the case where the alumina layer is in contact with a TiC x N y O z -layer.
  • the TiC x N y O z -layer can be an innermost layer of the coating.
  • the body is preferably a cutting tool insert of cemented carbide, titanium based carbonitride or ceramics.
  • the alumina layer can have a fine-grained microstructure of alumina grains with 80% or more of the alumina grains having a grain size of ⁇ 50% of an average grain size of the alumina layer. Also, the alumina layer can have a thickness of 4 to 8 ⁇ m and an average grain size of 1 to 3 ⁇ m.
  • the invention also provides a method of coating a body with an ⁇ alumina coating, comprising steps of: contacting a body with a hydrogen carrier gas containing one or more halides of aluminum and a hydrolyzing and/or oxidizing agent at high temperature in a CVD-reactor atmosphere wherein oxidation potential of the reactor prior to nucleation of Al 2 O 3 is kept at a low level by minimizing a total concentration of H 2 O or other oxidizing species, carrying out nucleation of Al 2 O 3 by controlled sequencing of reactant gases such that CO 2 and CO are supplied to the reactor first in an N 2 and/or Ar atmosphere followed by supplying H 2 and AlCl 3 to the reactor, the nucleation being carried out at a temperature between 850°-1100° C.
  • the dopant can comprise H 2 S
  • the reactor temperature can be 950°-1000° C. during the nucleation step, and prior to the nucleation of Al 2 O 3 the concentration of H 2 O or other oxidizing species in the hydrogen carrier gas is maintained below 5 ppm.
  • the body preferably comprises a cutting tool insert of cemented carbide, titanium based carbonitride or ceramics, wherein the alumina layer has a fine-grained single phase ⁇ -microstructure with 80% or more of the alumina grains having a grain size of ⁇ 50% of an average grain size of the alumina layer, the alumina layer having a thickness of 4 to 8 ⁇ m and an average grain size of 1-3 ⁇ m.
  • the coated body can be used for machining by contacting a metal workpiece with a cutting tool and moving the metal workpiece and the cutting tool relative to each other.
  • the alumina layer consists of single phase ⁇ -microstructure textured in the (104)-direction with a texture coefficient larger than 1.5, the texture coefficient (TC) being defined as:
  • TC ⁇ ( hkl ) I ⁇ ( hkl ) I o ⁇ ( hkl ) ⁇ ⁇ 1 n ⁇ ⁇ ⁇ ⁇ ⁇ I ⁇ ( hkl ) I o ⁇ ( hkl ) ⁇ - 1
  • I(hkl) measured intensity of the (hkl) reflection
  • I o (hlk) standard intensity of the ASTM standard powder pattern diffraction data
  • n number of reflections used in the calculation and (hkl) reflections used are: (012), (104), (110), (113), (024), (116).
  • the metal workpiece can comprise a steel, stainless steel, cast iron or nodular cast iron workpiece.
  • the cutting tool insert can be of cemented carbide, titanium based carbonitride or ceramics and the alumina layer can have a fine-grained ⁇ -microstructure of alumina grains with 80% or more of the alumina grains having a grain size of ⁇ 50% of an average grain size of the alumina layer, the alumina layer having a thickness of 4 to 8 ⁇ m and an average grain size of 1 to 3 ⁇ m.
  • FIG. 1 is a photomicrograph of an Al 2 O 3 coating in accordance with the invention.
  • a cutting tool comprising a body of a hard alloy onto which a wear resistant coating has been deposited.
  • the coating comprises one or several refractory layers of which at least one layer is a dense, fine-grained and preferably textured Al 2 O 3 -layer of the polymorph ⁇ .
  • FIG. 1 shows a Scanning Electron Microscope (SEM) top-view micrograph at 1000X magnification of a typical Al 2 O 3 -coating according to the invention.
  • a coated cutting tool according to the present invention exhibits improved wear and toughness properties compared to prior art tools when used for machining metal workpieces especially when the surface of the tool has been further smoothened by wet blasting.
  • the alumina coated cutting tool insert provides improved cutting performance in machining steel, stainless steel, cast iron and nodular cast iron.
  • the invention also provides a method of applying onto a hard substrate or preferably onto a TiC x N y O z coating at least one single phase Al 2 O 3 layer of the polymorph with a desired microstructure and crystallographic texture using suitable nucleation and growth conditions such that the properties of the Al 2 O 3 layer are stabilized.
  • the coated tool comprises a substrate of a sintered cemented carbide body, cermet or a ceramic body preferably of at least one metal carbide in a metal binder phase.
  • the individual layers in the coating structure may be TiC or related carbide, nitride, carbonitride, oxycarbide and oxycarbonitride of a metal selected from the group consisting of metals in the Groups IVB, VB, and VIB of the Periodic Table, B, Al and Si and/or mixtures thereof.
  • At least one of the layers is in contact with the substrate.
  • the fine-grained microstructure comprises a narrow grain size distribution. Most often 80% of the Al 2 O 3 grains have a grain size of ⁇ 50% of the average grain-size.
  • the grain-size of the Al 2 O 3 -coating is determined from a SEM top view micrograph at 5000X magnification. Drawing three straight lines in random directions, the average distances between grain boundaries along the lines, are taken as a measure of the grain-size.
  • the Al 2 O 3 -layer according to the invention has a preferred crystal growth orientation in the (104) direction which is determined by X-ray Diffraction (XRD) measurements.
  • XRD X-ray Diffraction
  • a Texture Coefficient, TC can be defined in the following calculation:
  • TC ⁇ ( hkl ) I ⁇ ( hkl ) I o ⁇ ( hkl ) ⁇ ⁇ 1 n ⁇ ⁇ ⁇ ⁇ ⁇ I ⁇ ( hkl ) I o ⁇ ( hkl ) ⁇ - 1
  • I(hkl) measured intensity of the (hkl) reflection
  • I o (hkl) standard intensity of the ASTM standard powder pattern diffraction data
  • n number of reflections used in the calculation and (hkl) reflections used are: (012), (104), (110), (113), (024), (116).
  • TC for the set of (104) crystal planes is larger than 1.5, preferably larger than 2.5, and most preferably larger than 3.0.
  • the coated body according to the invention is further characterized by a surface roughness (R) (R a ) of the refractory coating of less than 0.3 ⁇ m over a measured length of 0.25 ⁇ m mm.
  • R a surface roughness of the refractory coating
  • the Al 2 O 3 -layer is an exposed outermost layer.
  • the textured Al 2 O 3 -coating according to the invention is obtained by careful control of the oxidation potential of the CVD-reactor atmosphere prior to the nucleation of Al 2 O 3 .
  • the total concentration level of H 2 O or other oxidizing species should preferably be below 5 ppm.
  • the nucleation of Al 2 O 3 is initiated by a controlled sequencing of the reactant gases as follows: CO 2 and CO are first entering the reactor in a H 2 free atmosphere (e.g., in the presence of N 2 or/and Ar); then, a mixture of H 2 and AlCl 3 is allowed into the reactor.
  • the temperature can be 850°-1100° C., preferably 950°-1000° C., during the nucleation.
  • Cemented carbide cutting inserts with the composition 6.5% Co, 8.5% cubic carbides and balance WC were coated with a 5.5 ⁇ m thick layer of TiCN.
  • a 6 ⁇ m thick layer of ⁇ -Al 2 O 3 was deposited.
  • the oxidation potential of the hydrogen carrier gas i.e., the water vapour concentration, was set to a low level, less than 5 ppm.
  • the oxidation potential of the hydrogen carrier gas i.e., the water vapour concentration
  • a hydrogen-free reaction gas mixture comprising N 2 , CO 2 and CO was first introduced into the CVD-reactor.
  • the reaction gases were sequentially added in the given order.
  • H 2 and AlCl 3 were allowed into the reactor.
  • H 2 S was used as a dopant.
  • Step 1 Step 2 CO 2 : 4% 4% AlCl 3 : 4% 4% CO: 2% — H 2 S — 0.2% HCl 1% 4% H 2 : balance balance Pressure: 55 mbar 100 mbar Temperature: 1000° C. 1000° C. Duration: 1 hr 7.5 hr.
  • the cemented carbide substrate of Sample A was coated with TiCN (5.5 ⁇ m) and Al 2 O 3 (6 ⁇ m) as set forth above except that the Al 2 O 3 process was carried out according to a prior art technique resulting in a mixture of coarse ⁇ -and fine ⁇ -Al 2 O 3 grains in the coating.
  • Coated tool inserts from Samples A and B were all wet blasted with 150 mesh Al 2 O 3 powder in order to smoothen the coating surface.
  • the cutting inserts were then tested with respect to edge line and rake face flaking in a facing operation in nodular cast iron (AISI 60-40-18. DIN GGG40).
  • the shape of the machined workpiece was such that the cutting edge is intermitted or impacted twice during each revolution.
  • the cutting inserts from Samples A and B were also tested with respect to edge line flaking in a facing operation in an alloyed steel (AISI 1518. W-no. 10580).
  • the shape of the machined workpiece was such that the cutting edge is intermitted or impacted three times during each revolution.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Cutting Tools, Boring Holders, And Turrets (AREA)
  • Chemical Vapour Deposition (AREA)
  • Drilling Tools (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Polishing Bodies And Polishing Tools (AREA)
  • Catalysts (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Furnace Housings, Linings, Walls, And Ceilings (AREA)

Abstract

A body such as a cutting tool coated with refractory single- or multilayers, wherein specific layers are characterized by a controlled microstructure and phase composition with crystal planes preferably grown in a preferential direction with respect to the surface of the coated body. The coating includes one or several refractory layers of which at least one layer is a dense, fine-grained layer of α-Al2O3 preferably textured in the (104) direction. The coated tool exhibits excellent surface finish and shows much improved wear and toughness properties compared to prior art objects when used for machining steel, cast iron and, particularly, when machining nodular cast iron.
REEXAMINATION RESULTS
The questions raised in reexamination proceedings Nos. 90/009,410 and 90/009,666, filed May 5, 2009 and Feb. 24, 2010 respectively, have been considered, and the results thereof are reflected in this reissue patent which constitutes the reexamination certificate required by 35 U.S.C. 307 as provided in 37 CFR 1.570(e) for ex parte reexaminations, and/or the reexamination certificate required by 35 U.S.C. 316 as provided in 37 CFR 1.997(e) for inter partes reexaminations.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS
The present application is a reissue of U.S. Pat. No. 5,766,782, which claims the benefit of priority to Swedish Application No. 9400089-0 filed Jan. 14, 1994.
FIELD OF THE INVENTION
The invention relates to a coated cutting tool for chip-forming machining, a method of making the tool and a method of machining metal with the tool.
BACKGROUND OF THE INVENTION
Chemical Vapour Deposition (CVD) of alumina on cutting tools has been an industrial practice for more than 15 years. The wear properties of Al2O3 as well as of other refractory materials have been discussed extensively in the literature.
The CVD-technique has also been used to produce coatings of other metal oxides, carbides and nitrides, the metal being selected from transition metals of the IVB, VB and VIB groups of the Periodic Table. Many of these compounds have found practical applications as wear resistant or protective coatings, but few have received as much attention as TiC, TiN and Al2O3.
Cemented carbide cutting tools coated with various types of Al2O3-coatings e.g., pure κ-Al2O3, mixtures of κ- and α-Al2O3 and very coarse-grained α-Al2O3 have been commercially available for many years. Al2O3 crystallizes in several different phases: α, κ, γ, β, θ, etc. The two most frequently occurring phases in CVD of wear resistant Al2O3-coatings are the thermodynamically stable, hexagonal α-phase and the metastable κ-phase. Generally, the κ-phase is fine-grained with a grain size in the range 0.5-2.0 μm and often exhibits a columnar coating morphology. Furthermore, κ-Al2O3 coatings are free from crystallographic defects and free from micropores or voids.
The α-Al2O3 grains are usually coarser with a grain size of 1-6 μm depending upon the deposition conditions. Porosity and crystallographic defects are in this case more common.
Often both α- and κ-phase are present in a CVD alumina coating deposited onto a cutting tool. In commercial cutting tools, Al2O3 is always applied on TiC coated carbide or ceramic substrates (see, e.g., U.S. Pat. No. 3,837,896, now U.S. Reissue Pat. No. 29,420) and therefore the interfacial chemical reactions between the TiC-surface and the alumina coating are of particular importance. In this context, the TiC layer should also be understood to include layers having the formula TiCxNyOz in which the carbon in TiC is completely or partly substituted by oxygen and/or nitrogen.
The practice of coating cemented carbide cutting tools with oxides to further increase their wear resistance is in itself well known as is evidenced in e.g., U.S. Reissue Pat. No. 29,420 and U.S. Pat. Nos. 4,399,168, 4,018,631, 4,490,191 and 4,463,033. These patents disclose oxide coated bodies and how different pretreatments e.g., of TiC-coated cemented carbide, enhance the adherence of the subsequently deposited oxide layer. Alumina coated bodies are further disclosed in U.S. Pat. Nos. 3,736,107, 5,071,696 and 5,137,774 wherein the Al2O3 layers comprise α, κ and/or α+κ combinations.
U.S. Pat. No. 4,619,866 to Smith describes a method for producing fast growing Al2O3 layers by utilizing a hydrolysis reaction of a metal halide under the influence of a dopant e.g., hydrogen sulphide (H2S) in the concentration range 0.01-0.2% at a CVD deposition temperature of 1000-1050° C. Under these process conditions, essentially two phases of Al2O3, the α and the κ phases, are produced. The resulting coating consists of a mixture of the smaller κ-grains and the larger α-grains. The process yields coatings with an even layer thickness distribution around the coated body.
Commonly owned Swedish Patent Application 9101953-9 (corresponding to U.S. patent application Ser. No. 07/902,721 filed Jun. 23, 1992, abandoned in favor of Ser. No. 08/238,341 filed May 5, 1994, the disclosures of which are hereby incorporated by reference) discloses a method of growing a fine-grained κ-alumina coating.
Commonly owned Swedish Patent Application No. 9203852-0 (corresponding to U.S. patent application Ser. No. 08/159,217 filed Nov. 30, 1993, the disclosure of which is hereby incorporated by reference) discloses a method for obtaining a fine-grained, (012)-textured α-Al2O3-coating. This particular Al2O3-coating applied on cemented carbide tools has been found particularly useful for machining of cast iron.
Commonly owned Swedish Patent Application No. 9304283-6 discloses a body with a coating comprising one or more refractory layers of which at least one layer is a layer of α-Al2O3 textured in the (110) direction. The alumina layer is essentially free of cooling cracks and comprises platelike grains with a length of 2-8 μm and a length/width-ratio of 1-10.
SUMMARY OF THE INVENTION
It is an object of this invention to avoid or alleviate the problems of the prior art.
It is also an object of this invention to provide an improved process for making coated bodies, the resulting coated bodies and methods for their use.
In one aspect of the invention there is provided a body such as a cutting tool insert at least partially coated with one or more refractory layers of which at least one layer is alumina, the alumina layer having a thickness of d=0.5-25 μm with grain size (s): 0.5 μm<s<1 μm for 0.5 μm<d<2.5 μm and 0.5 μm<s<4 μm for 2.5 μm<d<25 μm. The alumina layer consists of single phase α-structure textured in the (104)-direction with a texture coefficient larger than 1.5, the texture coefficient being defined as:
TC ( hkl ) = I ( hkl ) I o ( hkl ) { 1 n Σ I ( hkl ) I o ( hkl ) } - 1
where I(hkl)=measured intensity of the (hkl) reflection, Io(hkl)=standard intensity of the ASTM standard powder pattern diffraction data, n=number of reflections used in the calculation and (hkl) reflections used are: (012), (104), (110), (113), (024), (116). The texture coefficient can be greater than 2.5, preferably greater than 3.0.
The alumina layer is preferably an exposed outermost layer. However, other layers can be present such as in the case where the alumina layer is in contact with a TiCxNyOz-layer. The TiCxNyOz-layer can be an innermost layer of the coating. The body is preferably a cutting tool insert of cemented carbide, titanium based carbonitride or ceramics. The alumina layer can have a fine-grained microstructure of alumina grains with 80% or more of the alumina grains having a grain size of ±50% of an average grain size of the alumina layer. Also, the alumina layer can have a thickness of 4 to 8 μm and an average grain size of 1 to 3 μm.
The invention also provides a method of coating a body with an αalumina coating, comprising steps of: contacting a body with a hydrogen carrier gas containing one or more halides of aluminum and a hydrolyzing and/or oxidizing agent at high temperature in a CVD-reactor atmosphere wherein oxidation potential of the reactor prior to nucleation of Al2O3 is kept at a low level by minimizing a total concentration of H2O or other oxidizing species, carrying out nucleation of Al2O3 by controlled sequencing of reactant gases such that CO2 and CO are supplied to the reactor first in an N2 and/or Ar atmosphere followed by supplying H2 and AlCl3 to the reactor, the nucleation being carried out at a temperature between 850°-1100° C. and carrying out growth of the Al2O3 by adding a sulphur dopant to the reactant gases. According to various features of the process, the dopant can comprise H2S, the reactor temperature can be 950°-1000° C. during the nucleation step, and prior to the nucleation of Al2O3 the concentration of H2O or other oxidizing species in the hydrogen carrier gas is maintained below 5 ppm. Also, the body preferably comprises a cutting tool insert of cemented carbide, titanium based carbonitride or ceramics, wherein the alumina layer has a fine-grained single phase α-microstructure with 80% or more of the alumina grains having a grain size of ±50% of an average grain size of the alumina layer, the alumina layer having a thickness of 4 to 8 μm and an average grain size of 1-3 μm.
The coated body can be used for machining by contacting a metal workpiece with a cutting tool and moving the metal workpiece and the cutting tool relative to each other. The cutting tool comprises a body at least partially coated with one or more refractory layers of which at least one layer is alumina, the alumina layer having a thickness of d=0.5-25 μm with grain size (s) wherein 0.5 μm<s<1 μm for 0.5 μm<d<2.5 μm and 0.5 μm<s<4 μm for 2.5 μm<d<25 μm. The alumina layer consists of single phase α-microstructure textured in the (104)-direction with a texture coefficient larger than 1.5, the texture coefficient (TC) being defined as:
TC ( hkl ) = I ( hkl ) I o ( hkl ) { 1 n Σ I ( hkl ) I o ( hkl ) } - 1
where I(hkl)=measured intensity of the (hkl) reflection; Io(hlk)=standard intensity of the ASTM standard powder pattern diffraction data; n=number of reflections used in the calculation and (hkl) reflections used are: (012), (104), (110), (113), (024), (116). The metal workpiece can comprise a steel, stainless steel, cast iron or nodular cast iron workpiece. The cutting tool insert can be of cemented carbide, titanium based carbonitride or ceramics and the alumina layer can have a fine-grained α-microstructure of alumina grains with 80% or more of the alumina grains having a grain size of ±50% of an average grain size of the alumina layer, the alumina layer having a thickness of 4 to 8 μm and an average grain size of 1 to 3 μm.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a photomicrograph of an Al2O3 coating in accordance with the invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
According to the invention there is provided a cutting tool comprising a body of a hard alloy onto which a wear resistant coating has been deposited. The coating comprises one or several refractory layers of which at least one layer is a dense, fine-grained and preferably textured Al2O3-layer of the polymorph α. FIG. 1 shows a Scanning Electron Microscope (SEM) top-view micrograph at 1000X magnification of a typical Al2O3-coating according to the invention.
A coated cutting tool according to the present invention exhibits improved wear and toughness properties compared to prior art tools when used for machining metal workpieces especially when the surface of the tool has been further smoothened by wet blasting. The alumina coated cutting tool insert provides improved cutting performance in machining steel, stainless steel, cast iron and nodular cast iron.
The invention also provides a method of applying onto a hard substrate or preferably onto a TiCxNyOz coating at least one single phase Al2O3 layer of the polymorph with a desired microstructure and crystallographic texture using suitable nucleation and growth conditions such that the properties of the Al2O3 layer are stabilized.
More specifically, the coated tool comprises a substrate of a sintered cemented carbide body, cermet or a ceramic body preferably of at least one metal carbide in a metal binder phase. The individual layers in the coating structure may be TiC or related carbide, nitride, carbonitride, oxycarbide and oxycarbonitride of a metal selected from the group consisting of metals in the Groups IVB, VB, and VIB of the Periodic Table, B, Al and Si and/or mixtures thereof. At least one of the layers is in contact with the substrate. However, at least one of the layers in the coating structure comprises a fine-grained, dense, single phase α-Al2O3 coating free of microporosity and crystallographic defects. This coating is preferentially textured with a thickness of d=0.5-25 μm with an average grain size (s) of:
    • 0.5 μm<s<1 μm for 0.5 μm<d<2.5 μm and
    • 0.5 μm<s<4 μm for 2.5 μm<d<25 μm.
The fine-grained microstructure comprises a narrow grain size distribution. Most often 80% of the Al2O3 grains have a grain size of ±50% of the average grain-size.
The grain-size of the Al2O3-coating is determined from a SEM top view micrograph at 5000X magnification. Drawing three straight lines in random directions, the average distances between grain boundaries along the lines, are taken as a measure of the grain-size.
The Al2O3-layer according to the invention has a preferred crystal growth orientation in the (104) direction which is determined by X-ray Diffraction (XRD) measurements. A Texture Coefficient, TC, can be defined in the following calculation:
TC ( hkl ) = I ( hkl ) I o ( hkl ) { 1 n Σ I ( hkl ) I o ( hkl ) } - 1
where I(hkl)=measured intensity of the (hkl) reflection; Io(hkl)=standard intensity of the ASTM standard powder pattern diffraction data; n=number of reflections used in the calculation and (hkl) reflections used are: (012), (104), (110), (113), (024), (116).
According to the invention TC for the set of (104) crystal planes is larger than 1.5, preferably larger than 2.5, and most preferably larger than 3.0.
The coated body according to the invention is further characterized by a surface roughness (R) (Ra) of the refractory coating of less than 0.3 μm over a measured length of 0.25 μm mm. Preferably, the Al2O3-layer is an exposed outermost layer.
The textured Al2O3-coating according to the invention is obtained by careful control of the oxidation potential of the CVD-reactor atmosphere prior to the nucleation of Al2O3. The total concentration level of H2O or other oxidizing species should preferably be below 5 ppm. However, the nucleation of Al2O3 is initiated by a controlled sequencing of the reactant gases as follows: CO2 and CO are first entering the reactor in a H2 free atmosphere (e.g., in the presence of N2 or/and Ar); then, a mixture of H2 and AlCl3 is allowed into the reactor. The temperature can be 850°-1100° C., preferably 950°-1000° C., during the nucleation. However, the exact conditions depend to a certain extent on the design of the equipment used. It is within the purview of the skilled artisan to determine whether the requisite texture and coating morphology have been obtained and to modify the nucleation and the deposition conditions in accordance with the present specification, if desired, to effect the amount of texture and coating morphology.
The following examples are provided to illustrate various aspects of the invention, it being understood that the same are intended only as illustrative and in nowise limitative.
EXAMPLE 1 Sample A
Cemented carbide cutting inserts with the composition 6.5% Co, 8.5% cubic carbides and balance WC were coated with a 5.5 μm thick layer of TiCN. In subsequent process steps during the same coating cycle, a 6 μm thick layer of α-Al2O3 was deposited. Prior to the nucleation, the oxidation potential of the hydrogen carrier gas, i.e., the water vapour concentration, was set to a low level, less than 5 ppm. For instance, see U.S. Pat. No. 5,071,696, the disclosure of which is hereby incorporated by reference.
A hydrogen-free reaction gas mixture comprising N2, CO2 and CO was first introduced into the CVD-reactor. The reaction gases were sequentially added in the given order. After a preset time, H2 and AlCl3 were allowed into the reactor. During the deposition of Al2O3, H2S was used as a dopant.
The gas mixtures and other process conditions during the Al2O3 deposition steps are set forth in Table 1.
TABLE 1
Process Condition Step 1 Step 2
CO2: 4% 4%
AlCl3: 4% 4%
CO: 2%
H2S 0.2%  
HCl 1% 4%
H2: balance balance
Pressure: 55 mbar 100 mbar
Temperature: 1000° C. 1000° C.
Duration: 1 hr 7.5 hr.
XRD-analysis of Sample A showed a texture coefficient, TC(104), of 3.2 of the (104) planes in the single in phase of the Al2O3 coating. SEM-studies of Sample A showed a fine-grained, 6 μm thick Al2O3-coating with an average grain size of 2.1 μm.
Sample B
The cemented carbide substrate of Sample A was coated with TiCN (5.5 μm) and Al2O3 (6 μm) as set forth above except that the Al2O3 process was carried out according to a prior art technique resulting in a mixture of coarse α-and fine κ-Al2O3 grains in the coating.
Coated tool inserts from Samples A and B were all wet blasted with 150 mesh Al2O3 powder in order to smoothen the coating surface. The cutting inserts were then tested with respect to edge line and rake face flaking in a facing operation in nodular cast iron (AISI 60-40-18. DIN GGG40). The shape of the machined workpiece was such that the cutting edge is intermitted or impacted twice during each revolution.
Cutting data:
    • Speed=150 m/min.
    • Cutting Depth=2.0 mm and
    • Feed=0.1 mm/rev.
The inserts were run one cut over the face of the workpiece. The results are expressed in Table 2 as percentage of the edge line in cut that obtained flaking as well as the rake face area subjected to flaking in relation to total contact area between the rake face and the workpiece chip.
TABLE 2
Edge Line Rake Face
Sample Flaking (%) Flaking (%)
A (invention) 5 6
B (comparative) 90 86
EXAMPLE 2
The cutting inserts from Samples A and B were also tested with respect to edge line flaking in a facing operation in an alloyed steel (AISI 1518. W-no. 10580). The shape of the machined workpiece was such that the cutting edge is intermitted or impacted three times during each revolution.
Cutting data:
    • Speed=130-220 m/min.
    • Cutting Depth=2 mm and
    • Feed=0.2 mm/rev.
The inserts were run one cut over the face of the workpiece. The results in Table 3 are expressed as percentages of the edge line in cut that obtained flaking.
TABLE 3
Sample Edge Line Flaking (%)
A (invention) 0 (according to the invention)
B (comparative) 28
The foregoing has described the principles, preferred embodiments and modes of operation of the present invention. However, the invention should not be construed as being limited to the particular embodiments discussed. Thus, the above-described embodiments should be regarded as illustrative rather than restrictive, and it should be appreciated that variations may be made in those embodiments by workers skilled in the art without departing from the scope of the present invention as defined by the following claims.

Claims (30)

What is claimed is:
1. A body at least partially coated with one or more refractory layers of which at least one layer is alumina, said alumina layer having a thickness d of 0.5 μm≦d≦25 μm with a grain size (s) of
0.5 μm<s<4 μm;
said alumina layer consisting of single phase α-structure textured in the (104)-direction with a texture coefficient larger than 1.5 2.5, the texture coefficient (TC) being defined by calculation:
TC ( hkl ) = I ( hkl ) I 0 ( hkl ) { 1 n I ( hkl ) I 0 ( hkl ) } - 1
where
I(hkl)=measured intensity of the (hkl) reflection
Io(hkl)=standard intensity of the ASTM standard powder pattern diffraction data
n=number of reflections used in the calculation and (hkl) reflections used are: (012), (104), (110), (113), (024), (116),
said alumina layer being an exposed outermost layer in contact with a TiCxNyOz-layer.
2. A body according to claim 1, wherein said TiCxNyOz-layer is an innermost layer of the coating.
3. A body according to claim 1, wherein said body is a cutting tool insert of cemented carbide, titanium based carbonitride or other ceramics.
4. A body according to claim 1, wherein the texture coefficient is larger than 2.5.
5. A body according to claim 1, wherein the texture coefficient is larger than 3.0.
6. A body according to claim 1, wherein the alumina layer has a fine-grained microstructure of alumina grains with 80% or more of the alumina grains having a grain size of ±50% of an average grain size of the alumina layer.
7. A body according to claim 1, wherein the alumina layer has a thickness of 4 to 8 μm and an average grain size of 1 to 3 μm.
8. The coated body of claim 1, wherein the alumina layer has been deposited by a chemical vapor deposition process wherein H2S dopant is added to reactant gases during the deposition process.
9. The coated body of claim 1, wherein the alumina layer has been deposited during a chemical vapor deposition process wherein a sulfur dopant is added to reactant gases during the deposition process.
10. The coated body of claim 1, wherein the alumina layer has a surface roughness (Ra) of less than 0.3 μm over a measured length of 0.25 mm.
11. The coated body of claim 1, wherein the alumina layer has been smoothened by wet blasting.
12. The coated body of claim 1, wherein 0.5 μm<d<2.5 μm and the grain size is greater than 0.5 μm and less than 1 μm.
13. The coated body of claim 1, wherein 2.5 μm<d<25 μm and the grain size is greater than 0.5 μm and less than 4 μm.
14. The coated body of claim 1, wherein the texture coefficient is larger than 3.0 and the alumina layer has a fine-grained microstructure of alumina with 80% or more of the alumina grains having a grain size of ±50% of an average grain size of the alumina layer.
15. The coated body of claim 1, wherein the texture coefficient is larger than 3.0 and the alumina layer has a thickness d of 0.5 μm≦d≦2.5 μm and the grain size is greater than 0.5 μm and less than 1 μm.
16. The coated body of claim 1, wherein the texture coefficient is larger than 3.0 and the alumina layer has a thickness d of 2.5 μm<d<25 μm and the grain size is greater than 0.5 μm and less than 4 μm.
17. The coated body of claim 16, wherein said body is a cutting tool insert of cemented carbide, titanium based carbonitride or other ceramics.
18. A body at least partially coated with one or more refractory layers of which at least one layer is alumina, said alumina layer having a thickness 4 to 8 μm with an average grain size of 1 to 3 μm,
said alumina layer consisting of single phase α-structure textured in the (104)-direction with a texture coefficient larger than 3.0, the texture coefficient (TC) being defined by calculation:
TC ( hkl ) = I ( hkl ) I 0 ( hkl ) { 1 n I ( hkl ) I 0 ( hkl ) } - 1
where
I(hkl)=measured intensity of the (hkl) reflection
Io(hkl)=standard intensity of the ASTM standard powder pattern diffraction data
n=number of reflections used in the calculation and (hkl) reflections used are: (012), (104), (110), (113), (024), (116),
wherein the alumina layer is an exposed outermost layer in contact with an inner TiCxNyOz-layer.
19. The coated body claim 18, wherein the alumina layer has been smoothened by wet blasting.
20. The coated body of claim 18, wherein the alumina layer has a fine-grained microstructure of alumina grains with 80% or more of the alumina grains having a grain size of ±50% of the average grain size of the alumina layer.
21. A body at least partially coated with one or more refractory layers of which at least one layer is alumina, said alumina layer having a thickness d of 0.5 μm≦d≦25 μm with a grain size (s) of
0.5 μm<s<4 μm;
said alumina layer consisting of single phase α-structure textured in the (104)-direction with a texture coefficient larger than 3.0, the texture coefficient (TC) being defined by calculation:
TC ( hkl ) = I ( hkl ) I 0 ( hkl ) { 1 n I ( hkl ) I 0 ( hkl ) } - 1
where
I(hkl)=measured intensity of the (hkl) reflection
Io(hkl)=standard intensity of the ASTM standard powder pattern diffraction data
n=number of reflections used in the calculation and (hkl) reflections used are: (012), (104), (110), (113), (024), (116),
said alumina layer being an exposed outermost layer in contact with an innermost TiCxNyOz-layer, and
wherein the alumina layer has a fine-grained microstructure of alumina grains with 80% or more of the alumina grains having a grain size of ±50% of an average grain size of the alumina layer.
22. The coated body of claim 21, wherein the alumina layer has been smoothened by wet blasting.
23. A body at least partially coated with one or more refractory layers of which at least one layer is alumina, said alumina layer having a thickness d of 0.5 μm≦d≦25 μm with a grain size (s) of
0.5 μm<s<4 μm;
said alumina layer consisting of single phase α-structure textured in the (104)-direction with a texture coefficient larger than 3.0, the texture coefficient (TC) being defined by calculation:
TC ( hkl ) = I ( hkl ) I 0 ( hkl ) { 1 n I ( hkl ) I 0 ( hkl ) } - 1
where
I(hkl)=measured intensity of the (hkl) reflection
Io(hkl)=standard intensity of the ASTM standard powder pattern diffraction data
n=number of reflections used in the calculation and (hkl) reflections used are: (012), (104), (110), (113), (024), (116),
said alumina layer being an exposed outermost layer in contact with a TiCxNyOz-layer,
wherein the alumina layer has been deposited by a chemical vapor deposition process wherein H2S dopant is added to reactant gases during the deposition process.
24. The coated body of claim 23, wherein the TiCxNyOz-layer is an innermost layer.
25. The body according to claim 23, wherein said body is a cutting tool insert of cemented carbide, titanium based carbonitride or other ceramics.
26. The coated body of claim 23, wherein the texture coefficient is larger than 3.0 and the alumina layer has a fine-grained microstructure of alumina with 80% or more of the alumina grains having a grain size of ±50% of an average grain size of the alumina layer.
27. The coated body of claim 23, wherein the texture coefficient is larger than 3.0 and the alumina layer has a thickness d of 0.5 μm<d<2.5 μm and the grain size is greater than 0.5 μm and less than 1 μm.
28. The coated body of claim 23, wherein the texture coefficient is larger than 3.0 and the alumina layer has thickness d of 2.5 μm<d<25 μm and the grain size is an 0.5 μm and less than 4 μm.
29. The coated body of claim 23, wherein the alumina layer has been smoothened by wet blasting.
30. The coated body of claim 23, wherein the thickness of the alumina layer is 4 to 8 μm and an average grain size is 1 to 3 μm.
US12/222,440 1994-01-14 2008-08-08 Aluminum oxide coated cutting tool and method of manufacturing thereof Expired - Lifetime USRE44870E1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US12/222,440 USRE44870E1 (en) 1994-01-14 2008-08-08 Aluminum oxide coated cutting tool and method of manufacturing thereof

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
SE9400089 1994-01-14
SE9400089A SE502223C2 (en) 1994-01-14 1994-01-14 Methods and articles when coating a cutting tool with an alumina layer
US08/366,107 US5766782A (en) 1994-01-14 1994-12-29 Aluminum oxide coated cutting tool and method of manufacturing thereof
US12/222,440 USRE44870E1 (en) 1994-01-14 2008-08-08 Aluminum oxide coated cutting tool and method of manufacturing thereof

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US08/366,107 Reissue US5766782A (en) 1994-01-14 1994-12-29 Aluminum oxide coated cutting tool and method of manufacturing thereof

Publications (1)

Publication Number Publication Date
USRE44870E1 true USRE44870E1 (en) 2014-04-29

Family

ID=20392562

Family Applications (2)

Application Number Title Priority Date Filing Date
US08/366,107 Ceased US5766782A (en) 1994-01-14 1994-12-29 Aluminum oxide coated cutting tool and method of manufacturing thereof
US12/222,440 Expired - Lifetime USRE44870E1 (en) 1994-01-14 2008-08-08 Aluminum oxide coated cutting tool and method of manufacturing thereof

Family Applications Before (1)

Application Number Title Priority Date Filing Date
US08/366,107 Ceased US5766782A (en) 1994-01-14 1994-12-29 Aluminum oxide coated cutting tool and method of manufacturing thereof

Country Status (13)

Country Link
US (2) US5766782A (en)
EP (1) EP0738336B2 (en)
JP (1) JP4402171B2 (en)
KR (1) KR100348542B1 (en)
CN (1) CN1061702C (en)
AT (1) ATE179222T1 (en)
AU (1) AU1548095A (en)
BR (1) BR9506948A (en)
DE (1) DE69509218T3 (en)
IL (1) IL112206A (en)
RU (1) RU2131330C1 (en)
SE (1) SE502223C2 (en)
WO (1) WO1995019457A1 (en)

Families Citing this family (79)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SE502223C2 (en) 1994-01-14 1995-09-18 Sandvik Ab Methods and articles when coating a cutting tool with an alumina layer
SE514181C2 (en) 1995-04-05 2001-01-15 Sandvik Ab Coated carbide inserts for milling cast iron
USRE40005E1 (en) 1996-09-06 2008-01-15 Sandvik Intellectual Property Ab Coated cutting insert
SE509560C2 (en) * 1996-09-06 1999-02-08 Sandvik Ab Coated cemented carbide inserts for machining cast iron
US6015614A (en) * 1997-11-03 2000-01-18 Seco Tools Ab Cemented carbide body with high wear resistance and extra tough behavior
US6293739B1 (en) * 1998-04-14 2001-09-25 Sumitomo Electric Industries, Ltd. Coated cemented carbide cutting tool
JP3678924B2 (en) 1998-11-05 2005-08-03 日立ツール株式会社 Aluminum oxide coated tool
SE516017C2 (en) 1999-02-05 2001-11-12 Sandvik Ab Cemented carbide inserts coated with durable coating
SE519828C2 (en) 1999-04-08 2003-04-15 Sandvik Ab Cut off a cemented carbide body with a binder phase enriched surface zone and a coating and method of making it
SE9901244D0 (en) 1999-04-08 1999-04-08 Sandvik Ab Cemented carbide insert
WO2000079022A1 (en) * 1999-06-21 2000-12-28 Sumitomo Electric Industries, Ltd. Coated hard alloy
SE519339C2 (en) 2000-11-22 2003-02-18 Sandvik Ab Cutting tools coated with alumina and ways of manufacturing the same
US6813980B2 (en) * 2000-11-30 2004-11-09 Ngk Spark Plug Co., Ltd. Cutting tool and throw-away insert therefor
SE522736C2 (en) * 2001-02-16 2004-03-02 Sandvik Ab Aluminum-coated cutting tool and method for making the same
SE522735C2 (en) * 2001-05-30 2004-03-02 Sandvik Ab Aluminum oxide coated cutting tool
US7264668B2 (en) 2001-10-16 2007-09-04 The Chinese University Of Hong Kong Decorative hard coating and method for manufacture
SE526604C2 (en) * 2002-03-22 2005-10-18 Seco Tools Ab Coated cutting tool for turning in steel
SE525581C2 (en) * 2002-05-08 2005-03-15 Seco Tools Ab Cutting coated with alumina made with CVD
SE526526C3 (en) * 2003-04-01 2005-10-26 Sandvik Intellectual Property Ways of coating cutting with A1203 and a cutting tool with A1203
JP4446469B2 (en) 2004-03-12 2010-04-07 住友電工ハードメタル株式会社 Coated cutting tool
US7455918B2 (en) * 2004-03-12 2008-11-25 Kennametal Inc. Alumina coating, coated product and method of making the same
KR100600573B1 (en) * 2004-06-30 2006-07-13 한국야금 주식회사 Coating materials for a cutting tool/an abrasion resistance tool
SE528109C2 (en) * 2004-07-12 2006-09-05 Sandvik Intellectual Property Phantom inserts, especially for phase milling of steel sheet for oil pipes, and ways of manufacturing the same
DE102004044240A1 (en) * 2004-09-14 2006-03-30 Walter Ag Cutting tool with oxidic coating
SE528431C2 (en) * 2004-11-05 2006-11-14 Seco Tools Ab With aluminum oxide coated cutting tool inserts and method of making this
SE528432C2 (en) 2004-11-05 2006-11-14 Seco Tools Ab With aluminum oxide coated cutting tool inserts and method for making this
SE528430C2 (en) 2004-11-05 2006-11-14 Seco Tools Ab With aluminum oxide coated cutting tool inserts and method of making this
US7972714B2 (en) 2004-12-14 2011-07-05 Sumitomo Electric Hardmetal Corp. Coated cutting tool
JP4518260B2 (en) * 2005-01-21 2010-08-04 三菱マテリアル株式会社 Surface-coated cermet cutting tool whose hard coating layer exhibits excellent chipping resistance in high-speed intermittent cutting
SE528672C2 (en) * 2005-01-31 2007-01-16 Sandvik Intellectual Property Carbide inserts for durability-demanding short-hole drilling and ways of making the same
US20060219325A1 (en) * 2005-03-31 2006-10-05 Kabushiki Kaisha Kobe Seiko Sho (Kobe Steel, Ltd.) Method for producing alpha-alumina layer-formed member and surface treatment
SE529023C2 (en) * 2005-06-17 2007-04-10 Sandvik Intellectual Property Coated carbide cutter
SE0602723L (en) * 2006-06-16 2007-12-17 Sandvik Intellectual Property Coated insert
SE529200C2 (en) * 2005-11-21 2007-05-29 Sandvik Intellectual Property Coated cutting, method of making and use
JP4797608B2 (en) * 2005-12-02 2011-10-19 三菱マテリアル株式会社 Surface-coated cutting insert and manufacturing method thereof
BRPI0721411A2 (en) 2007-01-02 2013-01-29 Taegu Tec Ltd Surface treatment method for cutting tools
SE531670C2 (en) * 2007-02-01 2009-06-30 Seco Tools Ab Textured alpha-alumina coated cutting for metalworking
IL182344A (en) * 2007-04-01 2011-07-31 Iscar Ltd Cutting insert having ceramic coating
US8833174B2 (en) * 2007-04-12 2014-09-16 Colorado School Of Mines Piezoelectric sensor based smart-die structure for predicting the onset of failure during die casting operations
RU2347126C1 (en) * 2007-05-02 2009-02-20 Александр Георгиевич Чуйко Ball valve shut-off member and method of its production
US20090004449A1 (en) * 2007-06-28 2009-01-01 Zhigang Ban Cutting insert with a wear-resistant coating scheme exhibiting wear indication and method of making the same
US8080323B2 (en) * 2007-06-28 2011-12-20 Kennametal Inc. Cutting insert with a wear-resistant coating scheme exhibiting wear indication and method of making the same
SE532020C2 (en) * 2007-09-13 2009-09-29 Seco Tools Ab Coated cemented carbide inserts for milling applications and manufacturing methods
WO2009070107A1 (en) * 2007-11-28 2009-06-04 Sandvik Intellectual Property Ab Coated cutting tool insert
EP2085500B1 (en) * 2007-12-28 2013-02-13 Mitsubishi Materials Corporation Surface-coated cutting tool with hard coating layer having excellent abrasion resistance
SE532048C2 (en) 2008-03-07 2009-10-13 Seco Tools Ab Oxide coated cutting tool cutter for chip separating machining of steel
SE532050C2 (en) 2008-03-07 2009-10-13 Seco Tools Ab Oxide coated cutting tool cutter for chip separating machining of steel
SE532047C2 (en) 2008-03-07 2009-10-13 Seco Tools Ab Oxide coated cutting tool cutter for chip separating machining of cast iron
SE532049C2 (en) 2008-03-07 2009-10-13 Seco Tools Ab Oxide coated cutting tool cutter for chip separating machining of steel
DE102008013966A1 (en) * 2008-03-12 2009-09-17 Kennametal Inc. Hard material coated body
DE102008013965A1 (en) * 2008-03-12 2009-09-17 Kennametal Inc. Hard material coated body
JP5496205B2 (en) 2008-08-28 2014-05-21 コーニング インコーポレイテッド Abrasion resistant coating for tool dies
WO2011055813A1 (en) * 2009-11-06 2011-05-12 株式会社タンガロイ Coated tool
DE102010016465B4 (en) * 2010-04-15 2017-08-17 Ceranovis Gmbh Process for coating, coating composition and their use for catalytic exhaust gas purification
EP2395126A1 (en) 2010-06-08 2011-12-14 Seco Tools AB Textured alumina layer
EP2446988A1 (en) 2010-10-29 2012-05-02 Seco Tools AB Cutting tool insert with an alpha-alumina layer having a multi-components texture
WO2012079769A1 (en) 2010-12-17 2012-06-21 Seco Tools Ab Coated cubic boron nitride tool for machining applications
EP2708300B1 (en) * 2011-05-10 2017-03-08 Sumitomo Electric Hardmetal Corp. Surface-coated cutting tool
EP2591874B1 (en) * 2011-11-11 2018-05-16 Sandvik Intellectual Property AB Friction stir welding tool made of cemented tungsten carbid with Nickel and with a Al2O3 surface coating
US9993878B2 (en) * 2013-11-08 2018-06-12 Tungaloy Corporation Coated cutting tool
WO2015093530A1 (en) * 2013-12-17 2015-06-25 京セラ株式会社 Coated tool
KR101843453B1 (en) * 2014-01-27 2018-03-29 가부시키가이샤 탕가로이 Coated Cutting Tool
JP6752147B2 (en) 2014-01-30 2020-09-09 サンドビック インテレクチュアル プロパティー アクティエボラーグ Alumina coated cutting tool
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
KR101666284B1 (en) 2014-12-30 2016-10-13 한국야금 주식회사 Hard coated layer for cutting tools
CN106660139B (en) * 2015-08-28 2020-02-18 住友电工硬质合金株式会社 Surface-coated cutting tool and method for manufacturing same
WO2017061059A1 (en) * 2015-10-09 2017-04-13 住友電工ハードメタル株式会社 Surface-coated cutting tool and method for producing same
CN108698133B (en) * 2016-02-18 2020-05-05 株式会社泰珂洛 Coated cutting tool
JP6898361B2 (en) * 2016-06-21 2021-07-07 サンドビック インテレクチュアル プロパティー アクティエボラーグ CVD coated cutting tool
EP3263743A1 (en) 2016-06-29 2018-01-03 Sandvik Intellectual Property AB Cvd coated cutting tool
JP6635340B2 (en) * 2016-08-24 2020-01-22 住友電工ハードメタル株式会社 Surface coated cutting tool and method of manufacturing the same
JP6229911B1 (en) 2016-10-19 2017-11-15 株式会社タンガロイ Coated cutting tool
JP6229912B1 (en) 2016-10-21 2017-11-15 株式会社タンガロイ Coated cutting tool
JP6210346B1 (en) 2016-11-02 2017-10-11 株式会社タンガロイ Coated cutting tool
JP6210347B1 (en) * 2016-11-04 2017-10-11 株式会社タンガロイ Coated cutting tool
JP6210348B1 (en) 2016-11-08 2017-10-11 株式会社タンガロイ Coated cutting tool
US11020803B2 (en) * 2016-11-14 2021-06-01 Tungaloy Corporation Coated cutting tool
CN109112500B (en) 2017-06-22 2022-01-28 肯纳金属公司 CVD composite refractory coating and application thereof
JP6999585B2 (en) 2019-01-18 2022-01-18 株式会社タンガロイ Cover cutting tool

Citations (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3736107A (en) 1971-05-26 1973-05-29 Gen Electric Coated cemented carbide product
US3836392A (en) 1971-07-07 1974-09-17 Sandvik Ab Process for increasing the resistance to wear of the surface of hard metal cemented carbide parts subject to wear
US3837896A (en) 1971-11-12 1974-09-24 Sandvik Ab Sintered cemented carbide body coated with two layers
US3852594A (en) 1973-07-25 1974-12-03 Pepi Inc X-ray diffraction apparatus
US3914473A (en) 1971-05-26 1975-10-21 Gen Electric Method of making a coated cemented carbide product
US3967035A (en) 1973-03-12 1976-06-29 General Electric Company Coated cemented carbide product
US3977061A (en) 1973-09-17 1976-08-31 Sandvik Aktiebolag Cutting insert and method of making the same
US4018631A (en) 1975-06-12 1977-04-19 General Electric Company Coated cemented carbide product
USRE29420E (en) 1971-11-12 1977-09-27 Sandvik Aktiebolag Sintered cemented carbide body coated with two layers
US4180400A (en) 1977-06-09 1979-12-25 Sandvik Aktiebolag Coated cemented carbide body and method of making such a body
EP0032887A1 (en) 1980-01-21 1981-07-29 Sandvik Aktiebolag Method of preparing coated cemented carbide product and resulting product
EP0045291A1 (en) 1980-07-28 1982-02-03 Sandvik Aktiebolag Method of making a coated cemented carbide body and body produced in such a manner
US4341834A (en) 1976-07-10 1982-07-27 Mitsubishi Kinzoku Kabushiki Kaisha Coated super-hard alloy articles
JPS57137460A (en) 1981-02-18 1982-08-25 Sumitomo Electric Ind Ltd Coated superhard alloy tool
US4399168A (en) 1980-01-21 1983-08-16 Santrade Ltd. Method of preparing coated cemented carbide product
US4490191A (en) 1981-12-16 1984-12-25 General Electric Company Coated product and process
US4535469A (en) 1982-03-31 1985-08-13 U.S. Philips Corporation X-Ray analysis apparatus having an adjustable stray radiation slit
USRE32093E (en) 1971-05-26 1986-03-18 General Electric Company Aluminum oxide coated titanium-containing cemented carbide product
USRE32110E (en) 1971-05-26 1986-04-15 General Electric Co. Aluminum oxide coated cemented carbide product
US4619866A (en) 1980-07-28 1986-10-28 Santrade Limited Method of making a coated cemented carbide body and resulting body
US4698266A (en) 1985-11-18 1987-10-06 Gte Laboratories Incorporated Coated cemented carbide tool for steel roughing applications and methods for machining
US4698256A (en) 1984-04-02 1987-10-06 American Cyanamid Company Articles coated with adherent diamondlike carbon films
EP0403461A1 (en) 1989-06-16 1990-12-19 Sandvik Aktiebolag Coated cutting insert
US5123934A (en) 1989-09-04 1992-06-23 Nippon Steel Corporation Ceramics coated cemented-carbide tool with high-fracture resistance
US5137774A (en) 1989-07-13 1992-08-11 Seco Tools Ab Multi-oxide coated carbide body and method of producing the same
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
DE4110005A1 (en) 1991-03-27 1992-10-01 Krupp Widia Gmbh Composite body used for cutting tools - coated with fine crystalline alpha-aluminium oxide to improve adhesion, wear and corrosion resistance
WO1992017623A1 (en) 1991-03-27 1992-10-15 Krupp Widia Gmbh Composite body, its use and process for producing it
EP0523021A1 (en) 1991-06-25 1993-01-13 Sandvik Aktiebolag Method of manufacturing an alumina coated sintered body
DE4131307A1 (en) 1991-09-20 1993-03-25 Immelborn Hartmetallwerk Application of adhesive aluminium oxide coatings to sintered hard metal items - by CVD using two different vapour phase compsns.
EP0603144A1 (en) 1992-12-18 1994-06-22 Sandvik Aktiebolag Oxide coated cutting tool
US5766782A (en) 1994-01-14 1998-06-16 Sandvik Ab Aluminum oxide coated cutting tool and method of manufacturing thereof
US5980988A (en) 1993-12-23 1999-11-09 Sandvik Ab Alumina coated cutting tool

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB285936A (en) 1926-10-21 1928-02-21 Charles Cooper Improvements in and relating to the drying of fuel gases
DE2265603C2 (en) 1971-05-26 1983-02-03 General Electric Co., Schenectady, N.Y. Cutting insert with a non-metallic intermediate layer between the base body and the top coating and method for its manufacture
SE514181C2 (en) 1995-04-05 2001-01-15 Sandvik Ab Coated carbide inserts for milling cast iron

Patent Citations (39)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USRE32093E (en) 1971-05-26 1986-03-18 General Electric Company Aluminum oxide coated titanium-containing cemented carbide product
US3914473A (en) 1971-05-26 1975-10-21 Gen Electric Method of making a coated cemented carbide product
USRE32110E (en) 1971-05-26 1986-04-15 General Electric Co. Aluminum oxide coated cemented carbide product
US3736107A (en) 1971-05-26 1973-05-29 Gen Electric Coated cemented carbide product
US3836392A (en) 1971-07-07 1974-09-17 Sandvik Ab Process for increasing the resistance to wear of the surface of hard metal cemented carbide parts subject to wear
USRE29420E (en) 1971-11-12 1977-09-27 Sandvik Aktiebolag Sintered cemented carbide body coated with two layers
US3837896A (en) 1971-11-12 1974-09-24 Sandvik Ab Sintered cemented carbide body coated with two layers
US3967035A (en) 1973-03-12 1976-06-29 General Electric Company Coated cemented carbide product
US3852594A (en) 1973-07-25 1974-12-03 Pepi Inc X-ray diffraction apparatus
US3977061A (en) 1973-09-17 1976-08-31 Sandvik Aktiebolag Cutting insert and method of making the same
US4018631A (en) 1975-06-12 1977-04-19 General Electric Company Coated cemented carbide product
US4463033A (en) 1976-07-10 1984-07-31 Mitsubishi Kinzoku Kabushiki Kaisha Process for production of coated super-hard alloy articles
US4341834A (en) 1976-07-10 1982-07-27 Mitsubishi Kinzoku Kabushiki Kaisha Coated super-hard alloy articles
US4180400A (en) 1977-06-09 1979-12-25 Sandvik Aktiebolag Coated cemented carbide body and method of making such a body
US4399168A (en) 1980-01-21 1983-08-16 Santrade Ltd. Method of preparing coated cemented carbide product
EP0032887A1 (en) 1980-01-21 1981-07-29 Sandvik Aktiebolag Method of preparing coated cemented carbide product and resulting product
EP0045291A1 (en) 1980-07-28 1982-02-03 Sandvik Aktiebolag Method of making a coated cemented carbide body and body produced in such a manner
US4619866A (en) 1980-07-28 1986-10-28 Santrade Limited Method of making a coated cemented carbide body and resulting body
JPS57137460A (en) 1981-02-18 1982-08-25 Sumitomo Electric Ind Ltd Coated superhard alloy tool
US4490191A (en) 1981-12-16 1984-12-25 General Electric Company Coated product and process
US4535469A (en) 1982-03-31 1985-08-13 U.S. Philips Corporation X-Ray analysis apparatus having an adjustable stray radiation slit
US4698256A (en) 1984-04-02 1987-10-06 American Cyanamid Company Articles coated with adherent diamondlike carbon films
US4698266A (en) 1985-11-18 1987-10-06 Gte Laboratories Incorporated Coated cemented carbide tool for steel roughing applications and methods for machining
EP0403461A1 (en) 1989-06-16 1990-12-19 Sandvik Aktiebolag Coated cutting insert
US5071696A (en) 1989-06-16 1991-12-10 Sandvik Ab Coated cutting insert
US5543176A (en) 1989-06-16 1996-08-06 Sandvik Ab CVD of Al2 O3 layers on cutting inserts
US5137774A (en) 1989-07-13 1992-08-11 Seco Tools Ab Multi-oxide coated carbide body and method of producing the same
US5162147A (en) 1989-07-13 1992-11-10 Sandvik Ab Kappa-alumina oxide coated carbide body and method of producing the same
US5123934A (en) 1989-09-04 1992-06-23 Nippon Steel Corporation Ceramics coated cemented-carbide tool with high-fracture resistance
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
DE4110005A1 (en) 1991-03-27 1992-10-01 Krupp Widia Gmbh Composite body used for cutting tools - coated with fine crystalline alpha-aluminium oxide to improve adhesion, wear and corrosion resistance
WO1992017623A1 (en) 1991-03-27 1992-10-15 Krupp Widia Gmbh Composite body, its use and process for producing it
US5516588A (en) 1991-03-27 1996-05-14 Widia Gmbh Composite body, its use and a process for its production
EP0523021A1 (en) 1991-06-25 1993-01-13 Sandvik Aktiebolag Method of manufacturing an alumina coated sintered body
DE4131307A1 (en) 1991-09-20 1993-03-25 Immelborn Hartmetallwerk Application of adhesive aluminium oxide coatings to sintered hard metal items - by CVD using two different vapour phase compsns.
EP0603144A1 (en) 1992-12-18 1994-06-22 Sandvik Aktiebolag Oxide coated cutting tool
US5487625A (en) 1992-12-18 1996-01-30 Sandvik Ab Oxide coated cutting tool
US5980988A (en) 1993-12-23 1999-11-09 Sandvik Ab Alumina coated cutting tool
US5766782A (en) 1994-01-14 1998-06-16 Sandvik Ab Aluminum oxide coated cutting tool and method of manufacturing thereof

Non-Patent Citations (74)

* Cited by examiner, † Cited by third party
Title
"1976 Powder Diffraction File, Search Manual", Joint Committee on Powder Diffraction Standards, 1976, pp. iii, v, xiii, xiv.
A. Franks, "Some Developments and Applications of Microfocus X-ray Diffraction Techniques", Br. J. Appl. Phys., Issue 9, Sep. 1958, abstract only from IOP Publishing.
A. Layyous et al., "Low Pressure Chemical Vapor Deposition (CVD) on Oxide and Nonoxide Ceramic Cutting Tools", Journal De Physique, May 1989, pp. C5-423-C5-432.
Affidavit of Bonnie L. Davis in Support of Protest (2 pages).
Affidavit of Michael F. Beblo in Support of Protest (4 pages).
Affidavit of Zhigang Ban in Support of Protest (6 pages).
B. D. Cullity, "Diffraction II: Intensities of diffracted beams," Elements of X-ray Diffraction, 2nd Ed., 1978.
B. Lux, "Al2O3 Deposition of CVD", Fourth European Conference on CVD, 1983, pp. 379-384.
C. Barrett et al., "Chapter 9, Pole Figures and Orientation Determination", Structure of Metals 3rd Revised Edition Crystallographic Methods, Principles and Data, International Series on Materials Science and Technology, vol. 35, pp. 193-222.
C. Chatfield et al., "Microstructure of CVD Al2O3", Journal De Physique, pp. C5-337-C5-388, 1989.
C. Cheng et al., "Homogeneous Catalysis of he Water Gas Shift Reaction Using Rhodium Carbonyl Iodide", Journal of the American Chemical Society, vol. 99, No. 8, Apr. 13, 1977, pp. 2791-2792.
C. Colombier, "Investigation of Al2O3 Layers; Influence of Substrate and Gas Phase", Technical University of Vienna Dissertation, May 24, 1985, 76 pages.
C. Columbier, "Dissertation Untersuchung an Al2O3-CVD-Schichten; Einflulbeta von Substrat und Gasphase", Technical University of Vienna, May 24, 1985, 71 pages.
C. Columbier, "Dissertation Untersuchung an Al2O3-CVD-Schichten; Einflulβ von Substrat und Gasphase", Technical University of Vienna, May 24, 1985, 71 pages.
C. Lee et al., The Preferred Orientation, Microhardness, and Microstructure of Chemically Vapor Deposited TiC on Cemented Carbides, Eighth international Conference on Chemical Vapor Deposition, 1981, pp. 563-572.
C. Park et al., "Crystallographic Orientation and Surface Morphology of Chemical Vapor Deposited Al2O3" J. Electrochem. Soc.: Solid-State Science and Technology, vol. 130, No. 7, Jul. 1983, pp. 1607-1611.
C. Park et al., "The Effect of Reaction Condition on the Crystallographic Orientation and Surface Morphology of Chemical Vapor Deposited Al2O3", Fourth European Conference on Chemical Vapor Deposition, Fourth European Conference on Chemical Vapor Deposition, 1983, pp. 410-420.
C. Park et al., "The Effects of Reaction Parameters on the Deposition Characteristics in Al2O3 CVD", Fourth European Conference on Chemical Vapor Deposition, 1983, pp. 401-409.
C.-S. Park et al., "Crystallographic Orientation and Surface Morphology of Chemical Vapor Deposited Al2O3", Journal of the Electrochemical Society, vol. 130, No. 7, (Jul. 1983), pp. 1607-1611.
D. Selbmann et al., "Chemical Vapor Deposition of Al-Containing TiC- and Ti(O,C)-Hard Coatings", Journal De Physique, vol. 1, Sep. 1991, pp. C2-587-C2-592.
E. Fredericksson et al., "Phase Transformation During CVD of Aluminum Oxide," Journal De Physique, 1989, pp. C5-391-C5-399.
E.M. Passmore, et al., "Strength-Grain Size-Porosity Relations in Alumina", Journal of the American Ceramic Society, vol. 48, No. 1, Jan. 21, 1965, pp. 1-7.
G. L. Tingey, "Kinetics of the Water-Gas Equilibrium Reaction. I. The Reaction of Carbon Dioxide with Hydrogen", The Journal of Physical Chemistry, vol. 70, No. 5, May 1996, pp. 1406-1412.
G. Spitzlsperger et al., "Recharacterization of a Tungsten etch back process with special emphasis on PFC emission reduction and throughout optimization", SPIE Proceedings (Society of Photo-Optical Instrumentation Engineers), 2001, pp. 428-434.
H. Altena et al, "Influence of Trace Impurities on the Formation of alpha-Al2O3 CVD", Ninth European Conference on Chemical Vapor Deposition, 1984, pp. 451-458.
H. Altena et al, "Influence of Trace Impurities on the Formation of α-Al2O3 CVD", Ninth European Conference on Chemical Vapor Deposition, 1984, pp. 451-458.
H. Altena et al., "Formation of Whiskers on Al2O3 CVD Layers", Fourth European Conference on Chemical Vapor Deposition, 1983.
H. Altena et al., "Growth of alpha-Al2O3 on Single and Polycrystalline Alumina Substrates by CVD", Fourth European Conference on Chemical Vapor Deposition, 1983, pp. 435-443.
H. Altena et al., "Growth of α-Al2O3 on Single and Polycrystalline Alumina Substrates by CVD", Fourth European Conference on Chemical Vapor Deposition, 1983, pp. 435-443.
H. J. Bunge, "Experimental Techniques of Texture Analysis", Experimental Techniques of Texture Analysis, 1986, pp. 1-28.
H. S. Kalish, "The Effect of Different Coatings on Hardmetal Machining Performance", pp. 58-69.
I. Lhermitte-Sebire et al., "The Adhesion Between Physically Vapour-Deposited or Chemically Vapour-Deposited Alumina and TiC-Coated Cemented Carbides as Characterized by Auger Electron Spectroscopy and Scratch Testing," Thin Solid Films, vol. 138, 1986, pp. 221-233.
I. Lhermitte-Sebire et al., "The Chemical Vapour Deposition of Alumina From AlCl3-H2-CO2 on a Stoichiometric TiC Substrate: A Thermodynamic Approach", Journal of the Less-Common Metals, vol. 118, 1986, pp. 83-102.
Information Disclosure Statement, associated transmittal letter, and Form PTO-1449 of Feb. 1, 1996 (U.S. Appl. No. 08/366,107).
J. Kim et al., "Effect of Partial Pressure of the Reactant Gas on the Chemical Vapor Deposition of Al2O3", Thin Solid Films, vol. 97, (1982), pp. 97-106.
J. Lindström et al., "Preparation and Machining Properties of CVD Al2O3 Coated Cemented Carbide Tools with Various Intermediate Layers", Ninth International Conference on Chemical Vapor Deposition, 1984, pp. 689-708.
J. N. Lindström et al., "Non-Equilibrium Conditions for CVD of Alumina", Third European Conference on Chemical Vapor Deposition, 1980, pp. 208-217.
J. N. Lindström et al., "Nucleation of Al2O3 Layers on Cemented Carbide Tools", Fifth International Conference on Chemical Vapor Deposition, 1975, pp. 453-468.
J. N. Lindström et al., "Nucleation of Al2O3 Layers on Cemented Carbide Tools", J. Electrochem. Soc.: Solid-State Science and Technology, vol. 123, No. 4, Apr. 1976, pp. 555-559.
J. Saraie et al., "Chemical Vapor Deposition of Al2O3 Thin Films under Reduced Pressures", J. Electrochem Soc., vol. 132, No. 4, 1985, pp. 890-892.
Jae-Gon Kim et al., "Effect of Partial Pressure of the Reactant Gas on the Chemical Vapour Deposition of Al2O3", Thin Solid Films, vol. 97, Issue 1 (Nov. 1982), pp. 97-106.
K. J. van Oostrum, "CAD in Light Optics and Electron Opics", Phillips Technical Review, vol. 42, No. 3, 1985, abstract only from INSPEC.
K. J. van Oostrum, "Display of Electron Microscope Images Obtained by Beam Rocking", European Conference on Electrotechnics, 1974, abstract only from INSPEC.
Kennametal's Second Supplemental Invalidity Contentions in Civil Action No. 2:10-cv-654, 2011.
Kim et al., "Effect of Partial Pressure of the Reactant Gas on the Chemical Vapour Deposition of Al2O3", Thin Solid Films, 97 (1982) pp. 97-106.
L. C. McCandless et al., "Chemically Vapor Deposited Ceramic Coatings of Carbides and Oxides", Second International Conference on Chemical Vapor Deposition, 1970, pp. 423-441.
L. Hall et al., "Properties of Aluminum Oxide Films Obtained from Nitrous Oxide and Aluminum Trimethyl", Second International Conference on Chemical Vapor Deposition, 1970, pp. 637-649.
L. S. Kassel, "Thermodynamic Functions of Nitous Oxide and Carbon Dioxide", ACS Publications, vol. 56, 1934, pp. 1838-1842.
M. Danzinger et al., "Influence of CH4 and Ar on the Morphologies of Al2O3-CVD Coatings", Journal De Physique, vol. 1, Sep. 1991, pp. C2-571-C2-578.
M. Kornmann et al., "Nucleation of Alumina Layers on TiC and Cemented Carbides by Chemical Vapor Deposition", Journal of Crystal Growth, vol. 28, (1975), pp. 259-262.
M. Podob et al., "CVD Coatings for Improved Tool Life", pp. 479-490.
N. Reiter et al., "Progress in Coated Indexable Inserts for Milling", pp. 568-579.
P. Wong et al., "Epitaxial Growth of Al2O3 on Sapphire and Ruby Substrates by Chemical Vapor Deposition", Second International Conference on Chemical Vapor Deposition, 1970, pp. 803-816.
Park et al., "Crystallographic Orientation and Surface Morphology of Chemical Vapor Deposited Al2O3", J. Electrochem Soc., vol. 130 No. 7 (1983) pp. 1607-1611.
Park et al., "The Effect of Reaction Condition on the Crystallographic Orientation and Surface Morphology of Chemical Vapor Deposited Al2O3", Proceedings of the Fourth European Conference on Chemical Vapour Deposition, (1983) pp. 410-420.
Park et al., "The Effects of Reaction Parameters on the Deposition Characteristics in Al2O3 CVD", Proceedings of the Fourth European Conference on Chemical Vapour Deposition, (1983) pp. 401-409.
R. Colmet et al., "Thermodynamic and Experimental Analysis of Chemical Vapor Deposition of Alumina from AlCl3-H2-CO2 Gas Phase Mixtures", Eighth International Conference on Chemical Vapor Deposition, 1981, pp. 17-31.
R. Funk et al., "Coating of Cemented Carbide Cutting Tools with Alumina by Chemical Vapor Deposition", J. Electrochem. Soc.: Solid-State Science and Technology, vol. 123, No. 2, Feb. 1976, pp. 285-289.
R. Funk, et al., "Coating of Cemented Carbide Cutting Tools with Alumina by Chemical Vapor Deposition", pp. 469-484.
R. Porat, "Thermal Properties of Coating Materials and Their Effect on the Efficiency of Coated Cutting Tools", Eighth International Conference on Chemical Vapor Deposition, 1981, pp. 533-539.
S. A. Wilson, "Determination of Texture in Zircaloy Using Complete Pole Figures", Scand J. Metallurgy, vol. 18, 1989.
S. Lin, "Mass Spectrometric Analyses of Vapor in Chemical Vapor Deposition of Alumina", J. Electrochem. Soc.: Solid-State Science and Technology, vol. 122, No. 10, 1975, pp. 1405-1408.
S. Munekawa, "Application of X-Ray Diffraction Techniques to the Semiconductor Field", The Rigaku Journal, vol. 5, No. 2, 1988, pp. 31-34.
S. S. Chun et al., "Study on the Chemical Vapor Deposition of Al2O3 for Improving Wear Resistance of Sintered Caride Tools", 1981.
S. Vuorinen et al., "Characterization of alpha-Al2O3 and kappa-Al2O3 and alpha-kappa Multioxide Coatings on Cemented Carbides", Thin Solid Films, vol. 193/194, 1990, pp. 536-546.
S. Vuorinen et al., "Characterization of α-Al2O3 and κ-Al2O3 and α-κ Multioxide Coatings on Cemented Carbides", Thin Solid Films, vol. 193/194, 1990, pp. 536-546.
S. Vuorinen, "Microstructural Study of Alumina/TiC Coated Cemented Carbide", Fourth European Conference on Chemical Vapor Deposition, 1983, pp. 357-362.
S. Vuorinen, "TEM Study of TiC and Alumina/TiC Coatings on Cemented Carbides", Ninth European Conference on Chemical Vapor Deposition, 1984, pp. 719-727.
S. W. Choi et al., "Nucleation and Growth of Al2O3 on Si in the CVD Process", Ninth International Conference on Chemical Vapor Deposition, 1984, pp. 233-241.
Supplement to Reissue Declaration by Assignee executed Jul. 18, 2008 (U.S. Appl. No. 12/222,440).
T. Johannesson et al., "Factors Affecting the Initial Nucleation of Alumina on Cemented-Carbide Substrates in the CVD Process", J. Vac. Sci. Technology, vol. 12, No. 4, 1975, pp. 854-857.
T. Schmitt et al., "Influence of Temperature and Substrate on Al2O3 CVD from AlCl3/H2/CO2 Gas Mixtures", Fourth European Conference on Chemical Vapor Deposition, 1983, pp. 421-427.
T.C. Huang et al., "Derivation of d-values from Digitized X-ray and Synchrotron diffraction Data," Advances in X-ray Analysis, vol. 33, 1990, pp. 295-303.
W. A. Bryant et al., "Thickness Uniformity of CVD Al2O3 Coatings", Ninth International Conference on Chemical Vapor Deposition, 1984, pp. 709-713 and 716-718.

Also Published As

Publication number Publication date
BR9506948A (en) 1997-09-09
RU2131330C1 (en) 1999-06-10
EP0738336B1 (en) 1999-04-21
SE502223C2 (en) 1995-09-18
WO1995019457A1 (en) 1995-07-20
EP0738336A1 (en) 1996-10-23
DE69509218D1 (en) 1999-05-27
US5766782A (en) 1998-06-16
CN1138881A (en) 1996-12-25
JP4402171B2 (en) 2010-01-20
DE69509218T3 (en) 2008-01-03
ATE179222T1 (en) 1999-05-15
AU1548095A (en) 1995-08-01
DE69509218T2 (en) 1999-08-19
EP0738336B2 (en) 2007-07-11
JPH09507528A (en) 1997-07-29
IL112206A0 (en) 1995-03-15
SE9400089D0 (en) 1994-01-14
IL112206A (en) 1998-02-22
KR100348542B1 (en) 2002-10-04
SE9400089L (en) 1995-07-15
CN1061702C (en) 2001-02-07

Similar Documents

Publication Publication Date Title
USRE44870E1 (en) Aluminum oxide coated cutting tool and method of manufacturing thereof
US5980988A (en) Alumina coated cutting tool
EP0603144B1 (en) Oxide coated cutting tool
US5968595A (en) Oxide coated cutting tool with increased wear resistance and method of manufacture thereof
US5702808A (en) Al2 O2 -coated cutting tool preferably for near net shape machining
US7011867B2 (en) α-alumina coated cutting tool
US5674564A (en) Alumina-coated sintered body
US6902764B2 (en) Oxide coated cutting tool
EP1464727A2 (en) Oxide coated cutting tool
PL174004B1 (en) Tool having oxide film produced thereon and metrhod of producing such oxide film