SU963450A3 - Режущий инструмент - Google Patents
Режущий инструмент Download PDFInfo
- Publication number
- SU963450A3 SU963450A3 SU721848420A SU1848420A SU963450A3 SU 963450 A3 SU963450 A3 SU 963450A3 SU 721848420 A SU721848420 A SU 721848420A SU 1848420 A SU1848420 A SU 1848420A SU 963450 A3 SU963450 A3 SU 963450A3
- Authority
- SU
- USSR - Soviet Union
- Prior art keywords
- layer
- hard alloy
- carbide
- titanium carbide
- substrate
- Prior art date
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- 239000010410 layer Substances 0.000 claims description 47
- 239000000956 alloy Substances 0.000 claims description 31
- 229910045601 alloy Inorganic materials 0.000 claims description 31
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 claims description 21
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 claims description 14
- 239000000758 substrate Substances 0.000 claims description 13
- 239000010941 cobalt Substances 0.000 claims description 11
- 229910017052 cobalt Inorganic materials 0.000 claims description 11
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- 229910000831 Steel Inorganic materials 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000010959 steel Substances 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 2
- 238000005137 deposition process Methods 0.000 claims description 2
- UNASZPQZIFZUSI-UHFFFAOYSA-N methylidyneniobium Chemical compound [Nb]#C UNASZPQZIFZUSI-UHFFFAOYSA-N 0.000 claims description 2
- NFFIWVVINABMKP-UHFFFAOYSA-N methylidynetantalum Chemical compound [Ta]#C NFFIWVVINABMKP-UHFFFAOYSA-N 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 238000004663 powder metallurgy Methods 0.000 claims description 2
- 239000002344 surface layer Substances 0.000 claims description 2
- 229910003468 tantalcarbide Inorganic materials 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910000975 Carbon steel Inorganic materials 0.000 claims 1
- 239000010962 carbon steel Substances 0.000 claims 1
- 239000007787 solid Substances 0.000 claims 1
- RSAQARAFWMUYLL-UHFFFAOYSA-N tic-10 Chemical compound CC1=CC=CC=C1CN1C(CCN(CC=2C=CC=CC=2)C2)=C2C(=O)N2CCN=C21 RSAQARAFWMUYLL-UHFFFAOYSA-N 0.000 claims 1
- 239000002184 metal Substances 0.000 abstract 3
- 239000011230 binding agent Substances 0.000 abstract 2
- 239000011248 coating agent Substances 0.000 abstract 2
- 238000000576 coating method Methods 0.000 abstract 2
- 238000005524 ceramic coating Methods 0.000 abstract 1
- 238000000151 deposition Methods 0.000 abstract 1
- 150000004767 nitrides Chemical class 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical 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
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/32—Carbides
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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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical 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
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/32—Carbides
- C23C16/325—Silicon carbide
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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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical 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
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/34—Nitrides
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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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical 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
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/34—Nitrides
- C23C16/342—Boron nitride
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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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical 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
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/34—Nitrides
- C23C16/345—Silicon nitride
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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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical 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
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/36—Carbonitrides
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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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical 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
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/403—Oxides of aluminium, magnesium or beryllium
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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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical 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
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/405—Oxides of refractory metals or yttrium
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical 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 method of coating
- C23C16/448—Chemical 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 method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
- C23C16/4488—Chemical 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 method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials by in situ generation of reactive gas by chemical or electrochemical reaction
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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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- 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
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/922—Static electricity metal bleed-off metallic stock
- Y10S428/923—Physical dimension
- Y10S428/924—Composite
- Y10S428/926—Thickness of individual layer specified
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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
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- Y10S428/922—Static electricity metal bleed-off metallic stock
- Y10S428/9335—Product by special process
- Y10S428/938—Vapor deposition or gas diffusion
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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
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12014—All metal or with adjacent metals having metal particles
- Y10T428/12028—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, etc.]
- Y10T428/12049—Nonmetal component
- Y10T428/12056—Entirely inorganic
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Description
Изобретение относится к порошковой металлургии, в частности к ре-, жущим инструментам, выполненным из спеченных твердых сплавов.
Известен режущий инструмент, изготовленный из спеченного твердого сплава, содержащего карбид вольфрама и кобальт Г1]·
Наиболее близким к предлагаемому по технической сущности и достигаемому результату является режущий инструмент, содержащий подложку из спеченного твердого сплава на основе карбида вольфрама с кобальтом и поверхностный слой из карбида титана [2J.15 Недостатком известных режущих инструментов является их низкий срок службы.
Цель изобретения - повышение срока„ службы.
Поставленная цель достигается тем, что режущий инструмент, содержащий подложку из спеченного твердого сплава на основе карбида вольфра- 2$ ма с кобальтом и слой карбида титана, дополнительно содержит наружный рлой из окиси алюминия толщиной 0,8 - 2 мкм,при атом толщина слоя карбида титана составляет 2 - 5 мкм.
Нанесение слоев карбида титана~й окиси алюминия на спеченный твердый сплав осуществляют из газовой фазы.
Перед нанесением слоя карбида титана поверхность твердого сплава можно окислять или нитрировать. Возможно окисление слоя TiC перед нане’сением слоя окиси алюминия. Операция окисления проводится как самостоятель ная. j
Дпя повышения срока службы издения необходимо, чтобы слой карбида титана был однородным и имел хорошее сцепление с подложкой. Для обеспечения оптимальной структуры слоя карбида титана необходимо, чтобы скорость процесса осаждения была низкой.
Пример 1. На подложку из спеченного твердого сплава на основе карбида вольфрама, содержащего, вес.% кобальт 9,5; карбид титана 12,0; карбид тантала 6,0; карбид ниобия ' 4,0; карбид вольфрама - остальное, при 1100°С наносят слой карбида титана из газовой фазы, содержащей,%: TiClfl 10; СНд 8; Нг82. Нанесение слоя окиси алюминия осуществляют -при той же .температуре (1100°C) из газовой фазы, содержащей, %: Н^70; 5;
СО 20; А1С13 5.
Испытания резания углеродистой ( стали с 1% С (твердость по Бринелю 300 кг/ммг) при скорости резания _
160 м/мин, подаче 0,30 мм/об показы- 5 вают следующие значения срока службы + мкм
3,3
15,5
18,3 + мкм+
4,3
43,4 инструмента, мин Твердый сплав Твердый сплав + слой TiC, 4 '(прототип) Твердый сплав + слой Al^O-j, 4 мкм Твердый еллав + слой Al^Oj, 30 мкм Твердый сплав + слой TiC, 2 + слой АКО,, 2 мкм
Пример 2, На подложку из спеченного твердого сплава состава, Сб.%: кобальт 9,5; карбид титана 15,5; карбид вольфрама — -остальное, наносят сначала
TiC, затем фазы состава, приведенного 1, при 1100°С. При резаний слой слой А1^0 .>, из газовой в примере стали с твердостью, по Бринелю · 280 кг/мм^ при скорости резания 180 м/мин и подаче 0,3 мм/об установлен следующий срок службы инструмента, мин:
Твердый сплав + слой
TiC, ,5 мкм (прототип) 14,4 Твердый сплав + слой.
TiC, 5 мкм + слой
А1^0э, 0,8 мкм 63,5 'Как следует из приведенных данных, нанесение наружного слоя из окиси алюминия толщиной 0,8-2 мкм на подложку из спеченного твердого сплава на основе карбида вольфрама со слоем карбида титана толщиной 2-5 мкм повышает срок службы режущего инструмента в 2,8-4,3 раза.
Claims (2)
- Изобретение относитс к порошковой металлургии, в частности к ре-. жущим инструментам, выполненным из спеченных твердых сплавов. Известен режущий инструмент, изготовленный из спеченного твердого сплава, содержащего карбид вольфрама и кобальт TI }Наиболее близким к предлагаемому по технической сущности и достигаемому результату вл етс режущий инструмент, содержащий подложку из спеченного твердого сплава на основ карбида вольфрама с кобальтом и поверхностный слой из карбида титана Недостатком известных режущих ин струментов вл етс их низкий срок службы. Цель изобретени - повышение сро службы. Поставленна цель достигаетс тем, что режущий инструмент, содержащий подложку из спеченного твердо го сплава на основе карбида вольфра ма с кобальтом и слой карбида титана , дополнительно содержит наружный слой из окиси алюмини толщиной 0,8 - 2 мкм,при атом толщина сло к бида титана составл ет 2 -5мкм. Нанесение слоев карбида титана и окиси алюмини на спеченный твердый сплав осуществл ют из газовой фазы. Перед нанесением сло карбида титана поверхность твердого сплава можно окисл ть или нитрировать. Возможно окисление сло TiC перед нанесением сло окиси алюмини . Операци окислени проводитс как самосто тельна . ..: Дл повышени срока службы издени необходимо, чтобы слой карбида титана был однородным и имел хорошее сцепление с подложкой. Дл обеспечени оптимальной структуры сло карбида титана необходимо, чтобы скорость процесса осаждени была низкой. Пример 1. На подложку из спеченного твердого сплава на основе карбида вольфрама, содержащецо, вес.%1 кобальт 9,5; карбид титана 12,0j карбид тантала 6,0; карбид ниоби ;, 4,0; карбид вольфрама - остальное, при нанос т слой карбида титана из газовой фазы, содержащей,%: TiC 10; СНд 8; . Нанесение сло окиси алюмини осуществл ют При той же .температуре () из газовой фазы, содержащей, %: СО 5 СО 20; А1С15 5. Испытани резани углеродистой стали с 1% С (твердость по Бринел 300 кг/мм) при зкорости резани 1бО м/мин, подаче 0,30 мм/об пока вают следующие значени срока слу инструмента, мин: Твердый сплав 3,3 Твердый сплав + + слой Tie, 4 мкм { прототип) 15,5 Твердый сплав + + слой , Твердый сплав + + слой 30 мкм Твердый сплав + + слой TiC, 2 МКМ+ + слой , 2 мкм Пример 2, На подложку из спеченного твердого сплава состава, Об.%: кобальт 9,5; кар .бид титана 15,5; карбид вольфрама . остальное, нанос т сначала слой TiC, затем - слойА1а. газово фазы состава, дтриведенного в прим 1, при . При резаний стали твердостью, по Бринелю 280 кг/мм при скорости резани 180 м/мин и подаче 0,3 мм/об установлен следу ррок службы инструменту, мин: Твердый сплав + слой TiC, .5 мкм (прототип) 14,4 Твердый сплав + слой. Tie, 5 мкм + слой , 0,8 мкм63,5 /Как следует из приведенных данных, нанесение наружного сло из окиси алюмини толщиной 0,8-2 мкм на подложку из спеченного твердого сплава на основе карбида вольфрама со слоем карбида титана толщиной 2-5 мкм повышает срок службы режущего инструмента в 2,8-4,3 раза. Формула изобретени Режущий инструмент, содержащий подложку из спеченного твердого сплава на основе карбида вольфрама с кобальтом и слой из карбида титана, отличающийс тем, что, с целью повышени срока службы, он дополнительно содержит наружный слой из окиси алюмини толщиной 0,8-2 мкм, при этом толщина сло карбида титана составл ет 2-5 мкм. Источники информации, прин тые во внимание при экспертизе 1.Киффер Р., Шварцкопф п. Твергре сплавы. Металлургиздат. 1957, с. 503-505.
- 2. Oberflache, 1970, 1, S. 19-20.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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SE14479/71A SE357984B (ru) | 1971-11-12 | 1971-11-12 |
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SU963450A3 true SU963450A3 (ru) | 1982-09-30 |
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ID=20299184
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SU721848420A SU963450A3 (ru) | 1971-11-12 | 1972-11-10 | Режущий инструмент |
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US (1) | US3837896A (ru) |
JP (1) | JPS5213201B2 (ru) |
BR (1) | BR7207922D0 (ru) |
CA (1) | CA972233A (ru) |
DE (1) | DE2253745C3 (ru) |
ES (1) | ES408523A1 (ru) |
FR (1) | FR2170383A5 (ru) |
GB (1) | GB1394108A (ru) |
IT (1) | IT969848B (ru) |
PL (1) | PL79682B1 (ru) |
SE (1) | SE357984B (ru) |
SU (1) | SU963450A3 (ru) |
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-
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- 1971-11-12 SE SE14479/71A patent/SE357984B/xx unknown
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1972
- 1972-10-24 IT IT30858/72A patent/IT969848B/it active
- 1972-11-02 DE DE2253745A patent/DE2253745C3/de not_active Expired
- 1972-11-03 US US00303362A patent/US3837896A/en not_active Expired - Lifetime
- 1972-11-07 JP JP47111560A patent/JPS5213201B2/ja not_active Expired
- 1972-11-10 FR FR7239859A patent/FR2170383A5/fr not_active Expired
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- 1972-11-10 GB GB5208472A patent/GB1394108A/en not_active Expired
- 1972-11-10 SU SU721848420A patent/SU963450A3/ru active
- 1972-11-10 CA CA156,174A patent/CA972233A/en not_active Expired
- 1972-11-10 PL PL1972158798A patent/PL79682B1/pl unknown
- 1972-11-11 ES ES408523A patent/ES408523A1/es not_active Expired
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IT969848B (it) | 1974-04-10 |
DE2253745B2 (de) | 1975-07-31 |
GB1394108A (en) | 1975-05-14 |
JPS4859106A (ru) | 1973-08-18 |
DE2253745C3 (de) | 1982-01-21 |
JPS5213201B2 (ru) | 1977-04-13 |
BR7207922D0 (pt) | 1973-12-13 |
FR2170383A5 (ru) | 1973-09-14 |
ES408523A1 (es) | 1976-02-16 |
US3837896A (en) | 1974-09-24 |
PL79682B1 (ru) | 1975-06-30 |
SE357984B (ru) | 1973-07-16 |
DE2253745A1 (de) | 1973-05-17 |
CA972233A (en) | 1975-08-05 |
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