JP5373781B2 - 多層金属酸化物被覆を有する工具とその被覆工具の製造方法 - Google Patents
多層金属酸化物被覆を有する工具とその被覆工具の製造方法 Download PDFInfo
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- 229910044991 metal oxide Inorganic materials 0.000 title claims description 59
- 150000004706 metal oxides Chemical class 0.000 title claims description 59
- 238000000576 coating method Methods 0.000 title claims description 54
- 239000011248 coating agent Substances 0.000 title claims description 48
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 238000005520 cutting process Methods 0.000 claims description 61
- 238000005240 physical vapour deposition Methods 0.000 claims description 58
- 238000000034 method Methods 0.000 claims description 53
- 229910052751 metal Inorganic materials 0.000 claims description 28
- 239000002184 metal Substances 0.000 claims description 28
- 238000007740 vapor deposition Methods 0.000 claims description 22
- 239000000758 substrate Substances 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 15
- 238000000151 deposition Methods 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 9
- 150000004767 nitrides Chemical class 0.000 claims description 9
- 230000008021 deposition Effects 0.000 claims description 8
- 238000007733 ion plating Methods 0.000 claims description 7
- 150000002739 metals Chemical class 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000000541 cathodic arc deposition Methods 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000010894 electron beam technology Methods 0.000 claims description 6
- 229910000997 High-speed steel Inorganic materials 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 229910000831 Steel Inorganic materials 0.000 claims description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 4
- 239000010959 steel Substances 0.000 claims description 4
- 239000011195 cermet Substances 0.000 claims description 3
- 238000001228 spectrum Methods 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims 1
- 230000000116 mitigating effect Effects 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 239000010410 layer Substances 0.000 description 67
- 238000001755 magnetron sputter deposition Methods 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 9
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- 238000003801 milling Methods 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 238000003754 machining Methods 0.000 description 3
- 230000000737 periodic effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- -1 HfAl Inorganic materials 0.000 description 2
- 229910010037 TiAlN Inorganic materials 0.000 description 2
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000011362 coarse particle Substances 0.000 description 2
- 239000002826 coolant Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- AZUYLZMQTIKGSC-UHFFFAOYSA-N 1-[6-[4-(5-chloro-6-methyl-1H-indazol-4-yl)-5-methyl-3-(1-methylindazol-5-yl)pyrazol-1-yl]-2-azaspiro[3.3]heptan-2-yl]prop-2-en-1-one Chemical compound ClC=1C(=C2C=NNC2=CC=1C)C=1C(=NN(C=1C)C1CC2(CN(C2)C(C=C)=O)C1)C=1C=C2C=NN(C2=CC=1)C AZUYLZMQTIKGSC-UHFFFAOYSA-N 0.000 description 1
- 229910001020 Au alloy Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910010038 TiAl Inorganic materials 0.000 description 1
- 229910008651 TiZr Inorganic materials 0.000 description 1
- 229910007880 ZrAl Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000003353 gold alloy Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000000992 sputter etching Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000005019 vapor deposition process Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
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- C—CHEMISTRY; METALLURGY
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- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
- C23C14/081—Oxides of aluminium, magnesium or beryllium
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
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- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
- C23C28/042—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material including a refractory ceramic layer, e.g. refractory metal oxides, ZrO2, rare earth oxides
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- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
- C23C28/044—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material coatings specially adapted for cutting tools or wear applications
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- C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
- C23C30/005—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process on hard metal substrates
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- C23C4/131—Wire arc spraying
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- Y—GENERAL 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
- Y10T428/2495—Thickness [relative or absolute]
- Y10T428/24967—Absolute thicknesses specified
- Y10T428/24975—No layer or component greater than 5 mils thick
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Ceramic Engineering (AREA)
- Physical Vapour Deposition (AREA)
- Cutting Tools, Boring Holders, And Turrets (AREA)
Description
・ターゲット: 丸いTi/Al(33/67原子%)源(直径63mm)
・80アンペア、495℃、3PaのN2圧力、40ボルト基材バイアス電圧
・ターゲット: 丸いAl源(直径63mm)
・80アンペア、495℃、0.7PaのO2圧力、70ボルト基材バイアス電圧
・ターゲット: Al
・10kWスパッタリング出力、495℃、0.5PaのAr圧力、150ボルト基材バイアス電圧(単極、パルス化)
・ターゲット: 丸いZr源(直径63mm)
・80アンペア、495℃、0.7PaのO2圧力、70ボルト基材バイアス電圧
・ターゲット: Zr
・10kWスパッタリング出力、495℃、0.5PaのAr圧力、150ボルト基材バイアス電圧(単極、パルス化)
Claims (13)
- 基材本体とそれに適用された多層被覆とを有する切削工具であり、当該多層被覆の、一方が他方の上に配置された少なくとも2つの層が、同じ金属又は異なる金属の金属酸化物を含有し、又はその金属酸化物からなるものである切削工具であって、一方が他方の上に配置された当該少なくとも2つの金属酸化物層が、i)RMS、ii)アーク気相成長(arc-PVD)、iii)イオンプレーティング、iv)電子線気相成長、及びv)レーザー堆積、から選ばれる異なるPVD法により逐次的に作られていて、i)〜v)のそれぞれの方法の変形法が異なるPVD法を構成するものでなく、一方が他方の上に配置された前記少なくとも2つの金属酸化物層が中間層なしに互いに直接配置されており、一方が他方の上に配置された前記少なくとも2つの金属酸化物層が交互にγ−酸化アルミニウム及び酸化ジルコニウムを含み、一方が他方の上に配置された前記少なくとも2つの金属酸化物層の金属酸化物が異なる結晶構造を有することを特徴とする切削工具。
- 一方が他方の上に配置された前記少なくとも2つの金属酸化物層のうちの1つがRMSで作られ、その上かあるいはその下に配置される、一方が他方の上に配置された前記少なくとも2つの金属酸化物層のうちの他方がアーク気相成長(arc−PVD)により作られていることを特徴とする、請求項1記載の切削工具。
- 一方が他方の上に配置された前記少なくとも2つの金属酸化物層が、同じPVD装置における異なったPVDプロセスによって、一方が他方の上に配置された前記少なくとも2つの金属酸化物層を適用する間で切削工具本体をそのPVD装置から取り出すことなく、及び/又はPVDプロセスを行う際におけるPVD装置内の真空を一方が他方の上に配置された前記少なくとも2つの金属酸化物層を適用する間で軽減することなく、逐次的に作られていることを特徴とする、請求項1又は2記載の切削工具。
- 一方が他方の上に配置された前記少なくとも2つの金属酸化物層のうちの少なくとも一方が1種の金属だけの金属酸化物を有することを特徴とする、請求項1〜3の1つに記載の切削工具。
- 一方が他方の上に配置された前記少なくとも2つの金属酸化物層のうちの少なくとも一方が、周期系のIVa族からVIIa族までの元素及び/又はアルミニウム及び/又はケイ素の炭化物、窒化物、酸化物、炭窒化物、酸窒化物、酸炭化物、酸炭窒化物、ホウ化物、ボロ窒化物、ボロ炭化物、ボロ炭窒化物、ボロ酸窒化物、ボロ酸炭化物、ボロ酸炭窒化物、酸ボロ窒化物、前述の化合物の混合金属相及び相混合物からの少なくとも1つの二次的成分を更に有することを特徴とする、請求項1〜4の1つに記載の切削工具。
- 前記被覆が、周期系のIVa族からVIIa族までの元素及び/又はアルミニウム及び/又はケイ素の炭化物、窒化物、酸化物、炭窒化物、酸窒化物、酸炭化物、酸炭窒化物、ホウ化物、ボロ窒化物、ボロ炭化物、ボロ炭窒化物、ボロ酸窒化物、ボロ酸炭化物、ボロ酸炭窒化物、酸ボロ窒化物、前述の化合物の混合金属相及び相混合物からなる更なる硬質材料層を含むことを特徴とする、請求項1〜5の1つに記載の切削工具。
- 前記被覆の各層が10nm〜50μmの層厚さを有することを特徴とする、請求項1〜6の1つに記載の切削工具。
- 前記被覆が500と4000の間のビッカース硬さ(Hv)を有することを特徴とする、請求項1〜7の1つに記載の切削工具。
- 前記基材本体が超硬合金、サーメット、鋼又は高速度鋼(HSS)から作られていることを特徴とする、請求項1〜8の1つに記載の切削工具。
- 一方が他方の上に直接配置された前記少なくとも2つの金属酸化物層の、XRD、XPS及び/又はTEMスペクトル中で最大の強度を有する相(主相)が異なる結晶構造を有することを特徴とする、請求項1〜9の1つに記載の切削工具。
- 基材本体とそれに適用された多層被覆とを有する切削工具であり、同じ金属又は異なる金属の金属酸化物が、一方が他方の上に配置された多層被覆の少なくとも2つの層で異なるPVD法により逐次的に適用されていて、一方が他方の上に配置された前記少なくとも2つの金属酸化物層が中間層なしに互いに直接配置されており、一方が他方の上に配置された前記少なくとも2つの金属酸化物層が交互にγ−酸化アルミニウム及び酸化ジルコニウムを含み、一方が他方の上に配置された前記少なくとも2つの金属酸化物層の金属酸化物が異なる結晶構造を有する切削工具の製造方法であって、前記PVD法が、i)RMS、ii)アーク気相成長(arc-PVD)、iii)イオンプレーティング、iv)電子線気相成長、及びv)レーザー堆積、から選ばれ、i)〜v)のそれぞれの方法の変形法が異なるPVD法を構成するものでない、切削工具製造方法。
- 一方が他方の上に配置された前記少なくとも2つの金属酸化物層のうちの1つをRMSにより適用し、その上かあるいはその下に配置される、一方が他方の上に配置された前記少なくとも2つの金属酸化物層のうちの別の1つを、アーク気相成長(arc−PVD)により適用することを特徴とする、請求項11記載の方法。
- 一方が他方の上に配置された前記少なくとも2つの金属酸化物層を、同じPVD装置における異なるPVDプロセスによって、一方が他方の上に配置された前記少なくとも2つの金属酸化物層を適用する間で前記切削工具本体をそのPVD装置から取り出すことなく、及び/又はPVDプロセスを行う際におけるPVD装置内の真空を一方が他方の上に配置された前記少なくとも2つの金属酸化物層を適用する間で軽減することなく、逐次的に適用することを特徴とする、請求項11又は12記載の方法。
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| Application Number | Priority Date | Filing Date | Title |
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| DE102007030735A DE102007030735A1 (de) | 2007-07-02 | 2007-07-02 | Werkzeug mit mehrlagiger Metalloxidbeschichtung |
| DE102007030735.9 | 2007-07-02 | ||
| PCT/EP2008/056037 WO2009003755A2 (de) | 2007-07-02 | 2008-05-16 | Werkzeug mit mehrlagiger metalloxidbeschichtung und verfahren zum herstellen des beschichteten werkzeugs |
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| JP2010531741A JP2010531741A (ja) | 2010-09-30 |
| JP5373781B2 true JP5373781B2 (ja) | 2013-12-18 |
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| EP (1) | EP2171121B1 (ja) |
| JP (1) | JP5373781B2 (ja) |
| KR (1) | KR101505222B1 (ja) |
| CN (1) | CN101720362A (ja) |
| DE (1) | DE102007030735A1 (ja) |
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| WO (1) | WO2009003755A2 (ja) |
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| JP4584356B2 (ja) * | 2008-12-26 | 2010-11-17 | キヤノンアネルバ株式会社 | 基板処理方法、基板処理装置、mos−fetの製造方法、不揮発メモリの製造方法、およびコンピュータ読み取り可能な記録媒体 |
| DE102009001675A1 (de) * | 2009-03-19 | 2010-09-23 | Eberhard-Karls-Universität Tübingen | Schneidwerkzeug |
| WO2013135364A2 (en) * | 2012-03-12 | 2013-09-19 | Oerlikon Trading Ag, Trübbach | Coating with enhanced sliding properties |
| DE102012017809A1 (de) * | 2012-09-10 | 2014-03-13 | Oerlikon Trading Ag, Trübbach | Verfahren zur Herstellung einer Metallborocarbidschicht auf einem Substrat |
| DE102014104672A1 (de) * | 2014-04-02 | 2015-10-08 | Kennametal Inc. | Beschichtetes Schneidwerkzeug und Verfahren zu seiner Herstellung |
| JP6789986B2 (ja) * | 2015-05-21 | 2020-11-25 | ヴァルター アーゲー | 多層アークpvdコーティングを有する工具 |
| DE102016108734B4 (de) | 2016-05-11 | 2023-09-07 | Kennametal Inc. | Beschichteter Körper und Verfahren zur Herstellung des Körpers |
| US10392690B1 (en) | 2019-02-13 | 2019-08-27 | Kuwait Institute For Scientific Research | Method for synthesizing a thin film stainless steel coating |
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| US4749629A (en) * | 1987-01-20 | 1988-06-07 | Gte Laboratories | Ultrathin laminated oxide coatings and methods |
| DE4405477A1 (de) | 1994-02-21 | 1995-08-24 | Hauzer Holding | PVD-Verfahren zur Abscheidung von mehrkomponentigen Hartstoffschichten |
| US5879823A (en) * | 1995-12-12 | 1999-03-09 | Kennametal Inc. | Coated cutting tool |
| DE19937284B4 (de) | 1999-08-06 | 2008-10-30 | GfO Gesellschaft für Oberflächentechnik mbH | Elektrisch leitender Mehrschichtaufbau |
| JP4502475B2 (ja) * | 2000-08-04 | 2010-07-14 | 株式会社神戸製鋼所 | 硬質皮膜および耐摩耗部材並びにその製造方法 |
| CN100413998C (zh) * | 2002-08-08 | 2008-08-27 | 株式会社神户制钢所 | α型晶体结构为主体的氧化铝被膜相关技术 |
| CN100419117C (zh) * | 2004-02-02 | 2008-09-17 | 株式会社神户制钢所 | 硬质叠层被膜、其制造方法及成膜装置 |
| JP2005262355A (ja) * | 2004-03-17 | 2005-09-29 | Sumitomo Electric Hardmetal Corp | 表面被覆切削工具 |
| JP2006028600A (ja) * | 2004-07-16 | 2006-02-02 | Kobe Steel Ltd | 耐摩耗性と耐熱性に優れた積層皮膜 |
| DE102004044240A1 (de) * | 2004-09-14 | 2006-03-30 | Walter Ag | Schneidwerkzeug mit oxidischer Beschichtung |
| JP2006192543A (ja) * | 2005-01-14 | 2006-07-27 | Sumitomo Electric Hardmetal Corp | 表面被覆切削工具およびその製造方法 |
| SE528891C2 (sv) * | 2005-03-23 | 2007-03-06 | Sandvik Intellectual Property | Skär belagt med ett multiskikt av metaloxid |
| US8119226B2 (en) * | 2006-10-18 | 2012-02-21 | Sandvik Intellectual Property Ab | Coated cutting tool |
| EP1914331B1 (en) * | 2006-10-18 | 2019-07-24 | Sandvik Intellectual Property AB | Coated cutting tool |
| CN101368260A (zh) * | 2007-09-14 | 2009-02-18 | 山特维克知识产权股份有限公司 | 用于在基底上沉积涂层的方法和设备 |
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| Publication number | Publication date |
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| US8871362B2 (en) | 2014-10-28 |
| US20100189978A1 (en) | 2010-07-29 |
| DE102007030735A1 (de) | 2009-01-08 |
| CN101720362A (zh) | 2010-06-02 |
| EP2171121A2 (de) | 2010-04-07 |
| EP2171121B1 (de) | 2014-10-01 |
| JP2010531741A (ja) | 2010-09-30 |
| ES2525702T3 (es) | 2014-12-29 |
| KR20100034013A (ko) | 2010-03-31 |
| WO2009003755A2 (de) | 2009-01-08 |
| WO2009003755A3 (de) | 2009-10-15 |
| KR101505222B1 (ko) | 2015-03-23 |
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