# US 10,767,258 B2 · Hard titanium aluminum nitride coating, hard-coated tool, and their production methods > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,767,258 B2 - Document ID: US10767258B2 - Status: Granted - Kind: B2 - Application number: 15/770,946 - Filed: 2016-11-18 - Published: 2018-10-25 - Granted: 2020-09-08 - Earliest claimed: 2015-11-25 - Assignees: Mitsubishi Hitachi Tool Engineering, Ltd. - Applicants: Mitsubishi Hitachi Tool Engineering, Ltd. - Inventors: Yuuzoh Fukunaga; Masayuki Imai - Web page: https://patentgrep.com/patent/US10767258B2 ## CPC - C23C 16/34: Nitrides {(C23C16/303 takes precedence)} - B23B 27/148: {Composition of the cutting inserts} - C23C 16/45502: {Flow conditions in reaction chamber} - C23C 16/45508: {Radial flow} - C23C 16/45514: {Mixing in close vicinity to the substrate} - C23C 16/45574: {Nozzles for more than one gas} - C23C 16/45578: {Elongated nozzles, tubes with holes} - C23C 28/042: {including a refractory ceramic layer, e.g. refractory metal oxides, ZrO2, rare earth oxides} - C23C 28/044: {coatings specially adapted for cutting tools or wear applications} - B23B 2228/10: Coatings - C23C: COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL (making metal-coated products by extrusion B21C23/22; covering with metal by connecting pre-existing layers to articles, see the relevant places, e.g. B21D39/00, B23K; metallising of glass C03C; metallising mortars, concrete, artificial stone, ceramics or natural stone C04B41/00; enamelling of, or applying a vitreous layer to, metals C23D; treating metal surfaces or coating of metals by electrolysis or electrophoresis C25D; single-crystal film growth C30B; by metallising textiles D06M11/83; decorating textiles by locally metallising D06Q1/04) - B23B: TURNING; BORING (arrangements for copying or controlling B23Q) ## Abstract A titanium aluminum nitride coating having a columnar crystal structure, which is formed on a substrate, comprises high-Al TiAlN having an fcc structure, which has a composition represented by (Tix1, Aly1)N, wherein x1 and y1 are numbers meeting x1=0.005-0.1, and y1=0.995-0.9 by atomic ratio, and network-like, high-Ti TiAlN having an fcc structure, which has a composition represented by (Tix2, Aly2)N, wherein x2 and y2 are numbers meeting x2=0.5-0.9, and y2=0.5-0.1 by atomic ratio; the high-Al TiAlN being surrounded by the network-like, high-Ti TiAlN. ## Claims ### Claim 1 A hard titanium aluminum nitride coating having a columnar crystal structure, and comprising high-Al TiAlN having an fcc structure, which has a composition represented by (Tix1, Aly1)N, wherein x1 and y1 are numbers meeting x1=0.005-0.1, and y1=0.995-0.9 by atomic ratio, and network-like, high-Ti TiAlN having an fcc structure, which has a composition represented by (Tix2, Aly2)N, wherein x2 and y2 are numbers meeting x2=0.5-0.9, and y2=0.5-0.1 by atomic ratio; said high-Al TiAlN being surrounded by said network-like, high-Ti TiAlN, wherein said network-like means that said high-Ti TiAlN is distributed in a network form in a photomicrograph. ### Claim 2 (depends on 1) The hard titanium aluminum nitride coating according to claim 1, wherein said high-Al TiAlN has an average longitudinal cross section diameter of 2-50 nm and an average transverse cross section diameter of 10-300 nm. ### Claim 3 (depends on 1) The hard titanium aluminum nitride coating according to claim 1, wherein said columnar crystal has an average lateral cross section diameter of 0.1-1.2 μm. ### Claim 4 A hard-coated tool having a hard titanium aluminum nitride coating formed on a substrate, wherein said hard titanium aluminum nitride coating has a columnar crystal structure, and comprises high-Al TiAlN having an fcc structure, which has a composition represented by (Tix1, Aly1)N, wherein x1 and y1 are numbers meeting x1=0.005-0.1, and y1=0.995-0.9 by atomic ratio, and network-like, high-Ti TiAlN having an fcc structure, which has a composition represented by (Tix2, Aly1)N, wherein x2 and y2 are numbers meeting x2=0.5-0.9, and y2=0.5-0.1 by atomic ratio; said high-Al TiAlN being surrounded by said network-like, high-Ti TiAlN, wherein said network-like means that said high-Ti TiAlN is distributed in a network form in a photomicrograph. ### Claim 5 (depends on 4) The hard-coated tool according to claim 4, wherein said high-Al TiAlN has an average longitudinal cross section diameter of 2-50 nm and an average transverse cross section diameter of 10-300 nm. ### Claim 6 (depends on 4) The hard-coated tool according to claim 4, wherein said columnar crystal has an average lateral cross section diameter of 0.1-1.2 μm. ### Claim 7 A method for producing a hard titanium aluminum nitride coating by chemical vapor deposition, comprising (1) using a mixture gas A comprising a TiCl4 gas, an AlCl3 gas, an N2 gas, and an H2 gas, and a mixture gas B comprising an NH3 gas, an N2 gas, and an H2 gas as starting material gases; (2) rotating first and second nozzles arranged with different distances from a rotation axis; and (3) ejecting said mixture gas A and said mixture gas B separately from said first and second nozzles. ### Claim 8 (depends on 7) The method for producing a hard titanium aluminum nitride coating according to claim 7, wherein with the total amount of said mixture gases A and B as 100% by volume, the composition of said mixture gas A comprises 0.02-0.31% by volume of a TiCl4 gas, 0.15-0.8% by volume of an AlCl3 gas, and 3-40% by volume of an N2 gas, the balance being an H2 gas, and the composition of said mixture gas B comprises 0.4-1.9% by volume of an NH3 gas, and 2-26% by volume of an N2 gas, the balance being an H2 gas; and wherein a volume ratio H2(A)/H2(B) of the H2 gas in said mixture gas A to the H2 gas in said mixture gas B is 1-5. ### Claim 9 (depends on 7) The method for producing a hard titanium aluminum nitride coating according to claim 7, wherein the distance H1 from an opening of said first nozzle to said rotation axis is longer than the distance H2 from an opening of said second nozzle to said rotation axis; and wherein said mixture gas A is ejected from said first nozzle, and said mixture gas B is ejected from said second nozzle. ### Claim 10 (depends on 7) The method for producing a hard titanium aluminum nitride coating according to claim 7, wherein the distance H1 from an opening of said first nozzle to said rotation axis is longer than the distance H2 from an opening of said second nozzle to said rotation axis; and wherein said mixture gas B is ejected from said first nozzle, and said mixture gas A is ejected from said second nozzle. ### Claim 11 (depends on 9) The method for producing a hard titanium aluminum nitride coating according to claim 9, wherein a ratio H1/H2 of the distance H1 from an opening of said first nozzle to said rotation axis to the distance H2 from an opening of said second nozzle to said rotation axis is in a range of 1.5-3. ### Claim 12 (depends on 7) The method for producing a hard titanium aluminum nitride coating according to claim 7, wherein the reaction pressure is 3-6 kPa, and the reaction temperature is 750-830° C. ### Claim 13 A method for producing a hard-coated tool having a hard titanium aluminum nitride coating by chemical vapor deposition, comprising (1) using a mixture gas A comprising a TiCl4 gas, an AlCl3 gas, an N2 gas, and an H2 gas, and a mixture gas B comprising an NH3 gas, an N2 gas, and an H2 gas as starting material gases; (2) rotating first and second nozzles arranged with different distances from a rotation axis; (3) disposing a tool substrate around said first and second nozzles; and (4) ejecting said mixture gas A and said mixture gas B separately from said first and second nozzles. ### Claim 14 (depends on 13) The method for producing a hard-coated tool according to claim 13, wherein with the total amount of said mixture gases A and B as 100% by volume, the composition of said mixture gas A comprises 0.02-0.31% by volume of a TiCl4 gas, 0.15-0.8% by volume of an AlCl3 gas, and 3-40% by volume of an N2 gas, the balance being an H2 gas, and the composition of said mixture gas B comprises 0.4-1.9% by volume of an NH3 gas, and 2-26% by volume of an N2 gas, the balance being an H2 gas; and wherein a volume ratio H2(A)/H2(B) of the H2 gas in said mixture gas A to the H2 gas in said mixture gas B is 1-5. ### Claim 15 (depends on 13) The method for producing a hard-coated tool according to claim 13, wherein the distance H1 from an opening of said first nozzle to said rotation axis is longer than the distance H2 from an opening of said second nozzle to said rotation axis; and wherein said mixture gas A is ejected from said first nozzle, and said mixture gas B is ejected from said second nozzle. ### Claim 16 (depends on 13) The method for producing a hard-coated tool according to claim 13, wherein the distance H1 from an opening of said first nozzle to said rotation axis is longer than the distance H2 from an opening of said second nozzle to said rotation axis; and wherein said mixture gas B is ejected from said first nozzle, and said mixture gas A is ejected from said second nozzle. ### Claim 17 (depends on 15) The method for producing a hard-coated tool according to claim 15, wherein a ratio H1/H2 of the distance H1 from an opening of said first nozzle to said rotation axis to the distance H2 from an opening of said second nozzle to said rotation axis is in a range of 1.5-3. ### Claim 18 (depends on 13) The method for producing a hard-coated tool according to claim 13, wherein the reaction pressure is 3-6 kPa, and the reaction temperature is 750-830° C.