EP1500713A1 - Verfahren zur Herstellung eines feinkörnigen Hartmetalles - Google Patents

Verfahren zur Herstellung eines feinkörnigen Hartmetalles Download PDF

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Publication number
EP1500713A1
EP1500713A1 EP04014482A EP04014482A EP1500713A1 EP 1500713 A1 EP1500713 A1 EP 1500713A1 EP 04014482 A EP04014482 A EP 04014482A EP 04014482 A EP04014482 A EP 04014482A EP 1500713 A1 EP1500713 A1 EP 1500713A1
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EP
European Patent Office
Prior art keywords
nitrogen
sintering
temperature
furnace
inserts
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Granted
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EP04014482A
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English (en)
French (fr)
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EP1500713B1 (de
Inventor
Per Gustafson
Mats Waldenström
Susanne Norgren
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Sandvik Intellectual Property AB
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Sandvik Intellectual Property AB
Sandvik AB
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Priority claimed from SE0302131A external-priority patent/SE0302131D0/xx
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • C22C1/059—Making alloys comprising less than 5% by weight of dispersed reinforcing phases
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
    • C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
    • C22C29/08—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds based on tungsten carbide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
    • B22F2005/001—Cutting tools, earth boring or grinding tool other than table ware
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy

Definitions

  • the present invention relates to a method of making a fine grained cemented carbide. By performing the sintering at least partly in a nitrogen-containing atmosphere, a grain refined cemented carbide structure has been obtained.
  • Cemented carbide inserts with a grain refined structure are today used to a great extent for machining of steel, stainless steels and heat resistant alloys in applications with high demands on both toughness and wear resistance. Another important application is in microdrills for the machining of printed circuit board so called PCB-drills.
  • Common grain growth inhibitors include vanadium, chromium, tantalum, niobium and/or titanium or compounds involving these. When added, generally as carbides, they limit grain growth during sintering, but they also have undesirable side effects such as unfavorably affecting the toughness behaviour. Additions of vanadium or chromium are particularly detrimental and have to be kept on a very low level in order to limit their negative influence on the sintering behaviour. Both vanadium and chromium reduce the sintering activity often resulting in an uneven binder phase distribution and toughness reducing defects in the sintered structure. Large additions are also known to result in precipitation of embrittling phases in the WC/Co grain boundaries. According to WO 99/13120, the amount of grain growth inhibitors can be reduced if a carbon content of the cemented carbide close to eta-phase formation is chosen.
  • tungsten carbonitride can be produced by high pressure nitrogen treatment of a mixture of tungsten and graphite powder. The process is described in JP-A-03-208811 and JP-A-11-35327 and it is claimed that the resulting tungsten carbonitride powder can be used as a raw material for manufacturing of super hard alloys.
  • JP-A-11-152535 discloses a process to manufacture fine grained tungsten carbonitride - cobalt hard alloys using tungsten carbonitride as a raw material.
  • JP-A-10-324942 and JP-A-10-324943 disclose methods to produce ultra-fine grained cemented carbide by adding the grain growth inhibitors as nitrides. In order to avoid pore formation by denitrification of the nitrides sintering is performed in a nitrogen atmosphere.
  • Fig. 1 shows in about 1500X a typical example of the structure of a "pure" WC-Co grade, alloyed with nitrogen by sintering according to the invention.
  • Fig. 2 shows in about 1500X a typical example of the structure of the same grade sintered according to prior art.
  • Fig. 3 shows in about 1500X a typical example of the structure of the same grade, alloyed with nitrogen by sintering according to the invention, after sintering at reduced temperature.
  • Fig. 4 shows in about 1500X a typical example of the structure after conventional sintering at reduced temperature.
  • Fig. 5 shows in about 1200X a typical example of the structure of a Cr 3 C 2 containing WC-Co grade, alloyed with nitrogen by sintering according to the invention, after sintering at reduced temperature.
  • Fig. 6 shows in about 1200X a typical example of the structure of the same grade after conventional sintering at reduced temperature.
  • Fig. 7 shows in about 1200X a typical example of the structure of a "pure" submicron (0.25 ⁇ m) WC-Co grade, alloyed with nitrogen by sintering according to the invention.
  • Fig. 8 shows in about 1200X a typical example of the structure of the same grade sintered according to prior art.
  • Fig. 9 shows in about 1200X a typical example of the structure of a Cr 3 C 2 containing submicron 0.25 ⁇ m WC-Co grade, alloyed with nitrogen by sintering according to the invention.
  • Fig. 10 shows in about 1200X a typical example of the structure of the same grade after conventional sintering.
  • Fig. 11 shows in about 1200X a typical example of the structure of a Cr 3 C 2 containing submicron 0.6 ⁇ m WC-Co grade, alloyed with nitrogen by sintering according to the invention.
  • Fig. 12 shows in about 1200X a typical example of the structure of the same grade after conventional sintering.
  • the method according to the present invention comprises mixing, milling and pressing of tungsten carbide - cobalt bodies according to conventional powder metallurgical methods, followed by sintering in a process characterised by introduction of nitrogen at a pressure of more than 0.5 atm, preferably more than 0.75 atm, into the sintering atmosphere after dewaxing but before pore closure, preferably before 1000 °C.
  • the whole sintering process is performed in nitrogen.
  • the nitrogen is after pore closure replaced by a protective atmosphere of e.g. argon or vacuum.
  • the resulting sintered body is characterised by a grain refined structure, reduced grain size and less abnormal grains, in combination with an improved binder phase distribution compared to sintering according to normal practices with a nitrogen content of more than 0.03 weight-%, preferably more than 0.05 weight-%.
  • the cobalt content for these alloys should be in the range 4 to 15 weight-%, preferably 5 to 12 weight-%.
  • the average number of abnormal grains can be determined using inserts etched for 2 minutes at room temperature in Murakamis regent, examining the etched surface with optical microscope at 1500X, counting the number of abnormal grains on ten micrographs, taken randomly from the surface, and calculating the average number of abnormal grains per micrograph. Each micrograph corresponds to a surface area of 8360 ⁇ m 2 .
  • the average number of abnormal grains per micrograph, having a maximum length in any direction >15 ⁇ m is ⁇ 1.0, preferably ⁇ 0.7.
  • the average number of abnormal grains per micrograph, having a maximum length in any direction >20 ⁇ m is ⁇ 0.5.
  • the average number of abnormal grains per micrograph, having a maximum length in any direction >5 ⁇ m, is ⁇ 0.15.
  • the beneficial effect of nitrogen alloying has to be combined with an addition of conventional grain growth inhibitors from groups IVb, Vb and/or VIb of the periodic table, preferably Cr, V and/or Ta, most preferably Cr and/or Ta, either as pure metals or compounds thereof except the nitrides thereof, preferably compounds free of nitrogen, most preferably carbides.
  • the process of the invention works on pure WC-Co alloys as well as on WC-Co alloys containing grain growth inhibitors. But the most significant improvement regarding grain growth control has been seen for straight WC-Co alloys with a sintered average grain size of ⁇ 1.5 ⁇ m, preferably ⁇ 1 ⁇ m but larger than 0.5 ⁇ m where no further grain growth inhibitors are necessary.
  • the furnace was evacuated and refilled with a protective atmosphere of 10 mbar Argon and kept at 1370 °C for 30 minutes followed by increased Ar pressure 40 mbar and a temperature increase up to the final sintering temperature 1410 °C where the temperature was kept for an additional hour before cooling and opening of the furnace.
  • the structure in the cutting inserts consisted of comparably fine and uniform tungsten carbide grain size in combination with a good binder phase distribution, Fig. 1.
  • Example 2 (reference example to Example 1)
  • Pressed inserts from Example 1 were sintered in H 2 up to 450 °C for dewaxing, further in vacuum to 1370 °C, then filled with a protective gas of 10 mbar of Ar and kept at 1370 °C for 30 minutes followed by an increased Ar pressure of 40 mbar and a temperature increase up to the final sintering temperature 1410 °C where the temperature was kept for an additional hour before cooling and opening of the furnace.
  • the structure in the cutting inserts consisted of a comparably less fine and uniform tungsten carbide grain size in combination with a acceptable binder phase distribution, Fig. 2.
  • Pressed inserts from Example 1 were sintered in H 2 up to 450°C for dewaxing.
  • the furnace was evacuated and refilled with nitrogen up to a pressure of 0.8 atm. The temperature was kept constant at 450 °C during the nitrogen filling procedure. After completed filling, the temperature was increased to 1370 °C with a speed of 15 °C/min, keeping the nitrogen pressure constant.
  • the furnace was evacuated and refilled with a protective atmosphere of 10 mbar Argon. The actual sintering was limited to a 30 min hold at 1370 °C followed by cooling and opening of the furnace.
  • the structure in the cutting inserts consisted of comparably fine and uniform tungsten carbide grain size in combination with an acceptable binder phase distribution, Fig. 3.
  • Example 4 (reference example to Example 3)
  • Pressed inserts from Example 1 were sintered in H 2 up to 450°C for dewaxing, further in vacuum to 1370 °C.
  • the furnace was filled with a protective atmosphere of 10 mbar Argon. The actual sintering was limited to a 30 min hold at 1370 °C followed by cooling and opening of the furnace.
  • the structure in the cutting inserts consisted of a comparably less fine and uniform tungsten carbide grain size in combination with an unacceptable binder phase distribution, Fig. 4.
  • the structure in the cutting inserts consisted of comparably fine and uniform tungsten carbide grain size in combination with a good binder phase distribution, Fig. 5.
  • Example 6 (reference example to Example 5)
  • Pressed inserts from Example 5 were sintered in H 2 up to 450°C for dewaxing, further in vacuum to 1370 °C.
  • the furnace was filled with a protective atmosphere of 10 mbar Argon. The actual sintering was limited to a 30 min hold at 1370 °C followed by cooling and opening of the furnace.
  • the structure in the cutting inserts consisted of a comparably less fine and uniform tungsten carbide grain size in combination with an unacceptable binder phase distribution, Fig. 6.
  • the furnace was evacuated and refilled with a protective atmosphere of 10 mbar Argon and kept at 1370 °C for 30 minutes followed by an increased Ar pressure of 40 mbar and a temperature increase up to the final sintering temperature 1410 °C where the temperature was kept for an additional hour before cooling and opening of the furnace.
  • the structure in the cutting inserts consisted of compared to the reference in example 8 finer large tungsten carbide grains in combination with a good binder phase distribution, Fig. 7.
  • Example 8 (reference example to Example 7)
  • Pressed inserts from Example 7 were sintered in H 2 up to 450°C for dewaxing, further in vacuum to 1370 °C, then filled with an protective gas of 10 mbar of Ar and kept at 1370 °C for 30 minutes followed by an increased Ar pressure of 40 mbar and a temperature increase up to the final sintering temperature 1410 °C where the temperature was kept for an additional hour before cooling and opening of the furnace.
  • the structure in the cutting inserts consisted of large grains and a non-uniform tungsten carbide grain size in combination with an acceptable binder phase distribution, Fig. 8.
  • Example 7 and 8 Inserts from Example 7 and 8 were etched for 2 minutes at room temperature in Murakamis regent and examined under optical microscope at 1500X. Ten micrographs were taken. In all ten micrographs, WC grains having a length in any direction >15 ⁇ m were detected and the maximum length for each such grain was measured. An average number of abnormal grains per micrograph, corresponding to a surface area of 8360 ⁇ m 2 , was calculated by dividing the number of grains by 10. Result: Average number of grains with max. length >15 ⁇ m >20 ⁇ m >25 ⁇ m Example 7 (invention) 0.33 0 0 Example 8 (reference) 1.4 0.6 0.2
  • the furnace was evacuated and refilled with a protective atmosphere of 10 mbar Argon and kept at 1370 °C for 30 minutes followed by an increased Ar pressure of 40 mbar and a temperature increase up to the final sintering temperature of 1410 °C where the temperature was kept for an additional hour before cooling and opening of the furnace.
  • the structure in the cutting inserts consisted of a uniform submicron tungsten carbide grain size and in combination with an almost absence of large grains and a uniform Co distribution, Fig. 9.
  • Example 11 (reference example to Example 10)
  • Pressed inserts from Example 10 were sintered in H 2 up to 450°C for dewaxing, further in vacuum to 1370 °C, then filled with a protective gas of 10 mbar of Ar and kept at 1370 °C for 30 minutes followed by an increased Ar pressure of 40 mbar and a temperature increase up to the final sintering temperature 1410 °C where the temperature was kept for an additional hour before cooling and opening of the furnace.
  • the structure in the cutting inserts consisted of a less uniform submicron tungsten carbide grain size and in combination with some large WC grains, Fig. 10.
  • Example 10 and 11 Inserts from Example 10 and 11 were etched for 2 minutes at room temperature in Murakamis regent and examined under optical microscope at 1500X. Ten micrographs were taken. In all ten micrographs, WC grains having a length in any direction >5 ⁇ m were detected and the maximum length for each such grain was measured. An average number of abnormal grains per micrograph, corresponding to a surface area of 8360 ⁇ m 2 , was calculated by dividing the number of grains by 10. Result: Average number of grains with max. length >5 ⁇ m Example 10 (invention) 0-0.1 Example 11 (reference) 0.25-0.4
  • the furnace was evacuated and refilled with a protective atmosphere of 10 mbar Argon and kept at 1370 °C for 30 minutes followed by an increased Ar pressure of 40 mbar and a temperature increase up to the final sintering temperature of 1410 °C where the temperature was kept for an additional hour before cooling and opening of the furnace.
  • the structure in the cutting inserts consisted of a uniform submicron tungsten carbide grain size and in combination with an almost absence of large grains and a uniform Co distribution, Fig. 11.
  • Example 14 (reference example to Example 13)
  • Pressed inserts from Example 13 were sintered in H 2 up to 450 °C for dewaxing, further in vacuum to 1370 °C, then filled with a protective gas of 10 mbar of Ar and kept at 1370 °C for 30 minutes followed by an increased Ar pressure of 40 mbar and a temperature increase up to the final sintering temperature 1410 °C where the temperature was kept for an additional hour before cooling and opening of the furnace.
  • the structure in the cutting inserts consisted of a less uniform submicron tungsten carbide grain size and in combination with some large WC grains, Fig. 12.
  • Example 13 and 14 Inserts from Example 13 and 14 were etched for 2 minutes at room temperature in Murakamis regent and examined under optical microscope at 1500X. Ten micrographs were taken. In all ten micrographs, WC grains having a length in any direction >5 ⁇ m were detected and the maximum length for each such grain was measured. An average per micrograph was calculated by dividing the number of grains by 10. An average number of abnormal grains per micrograph, corresponding to a surface area of 8360 ⁇ m 2 , was calculated by dividing the number of grains by 10. Result: Average number of grains with max. length >5 ⁇ m Example 13 (invention) 0-0.1 Example 14 (reference) 0.2-0.4

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Powder Metallurgy (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Cutting Tools, Boring Holders, And Turrets (AREA)
  • Materials For Medical Uses (AREA)
EP04014482A 2003-07-25 2004-06-21 Verfahren zur Herstellung eines feinkörnigen Hartmetalles Expired - Lifetime EP1500713B1 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
SE0302131 2003-07-25
SE0302131A SE0302131D0 (sv) 2003-07-25 2003-07-25 Method of making a fine grained cemented carbide
SE0302835A SE527173C2 (sv) 2003-07-25 2003-10-28 Sätt att tillverka en finkorning hårdmetall
SE0302835 2003-10-28

Publications (2)

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EP1500713A1 true EP1500713A1 (de) 2005-01-26
EP1500713B1 EP1500713B1 (de) 2007-08-15

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US (2) US20050025657A1 (de)
EP (1) EP1500713B1 (de)
JP (1) JP2005042201A (de)
KR (1) KR101202225B1 (de)
AT (1) ATE370257T1 (de)
DE (1) DE602004008166T2 (de)
IL (1) IL162686A (de)
SE (1) SE527173C2 (de)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1935999A2 (de) 2006-12-15 2008-06-25 Sandvik Intellectual Property AB Beschichteter Hartmetallschaftfräser
EP2011890A1 (de) 2007-06-01 2009-01-07 Sandvik Intellectual Property AB Feinkörniges Hartmetall mit verfeinerter Struktur
US7976607B2 (en) 2006-06-15 2011-07-12 Sandvik Intellectual Property Ab Cemented carbide with refined structure
AT513422B1 (de) * 2012-09-13 2016-05-15 Tutec Gmbh Hexagonales WC-Pulver, Verfahren zu dessen Herstellung sowie Verwendung des Pulvers
DE112006000769C5 (de) 2005-03-28 2022-08-18 Kyocera Corporation Hartmetall und Schneidwerkzeug

Families Citing this family (9)

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Publication number Priority date Publication date Assignee Title
SE0700800L (sv) * 2006-12-15 2008-06-16 Sandvik Intellectual Property Belagt skärverktyg
SE0701761L (sv) 2007-06-01 2008-12-02 Sandvik Intellectual Property Finkornig hårdmetall för svarvning i varmhållfasta superlegeringar (HRSA) och rostfria stål
SE0701760L (sv) * 2007-06-01 2008-12-02 Sandvik Intellectual Property Hårdmetallskär för avstickning, spårstickning och gängning
US8455116B2 (en) 2007-06-01 2013-06-04 Sandvik Intellectual Property Ab Coated cemented carbide cutting tool insert
SE531971C2 (sv) * 2007-08-24 2009-09-15 Seco Tools Ab Belagt skärverktyg för allmän svarvning i varmhållfast superlegeringar (HRSA)
WO2014191505A1 (en) * 2013-05-31 2014-12-04 Sandvik Intellectual Property Ab New process of manufacturing cemented carbide and a product obtained thereof
RU2015156229A (ru) * 2013-05-31 2017-07-06 Сандвик Интеллекчуал Проперти Аб Новый способ получения цементированного карбида и получаемый при его помощи продукт
EP3086895B1 (de) * 2013-12-27 2020-04-08 Sandvik Intellectual Property AB Korrosionsbeständige duplexstahllegierung, daraus gefertigte objekte und verfahren zur herstellung der legierung
CN113322389A (zh) * 2021-06-01 2021-08-31 株洲硬质合金集团有限公司 一种耐磨损耐腐蚀超细硬质合金的烧结方法

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE112006000769C5 (de) 2005-03-28 2022-08-18 Kyocera Corporation Hartmetall und Schneidwerkzeug
US7976607B2 (en) 2006-06-15 2011-07-12 Sandvik Intellectual Property Ab Cemented carbide with refined structure
EP1935999A2 (de) 2006-12-15 2008-06-25 Sandvik Intellectual Property AB Beschichteter Hartmetallschaftfräser
EP2011890A1 (de) 2007-06-01 2009-01-07 Sandvik Intellectual Property AB Feinkörniges Hartmetall mit verfeinerter Struktur
EP2287355A1 (de) 2007-06-01 2011-02-23 Sandvik Intellectual Property AB Hartmetallwendeplatten zum Teilen, Rillen und Gewindeschneiden
US7938878B2 (en) 2007-06-01 2011-05-10 Sandvik Intellectual Property Ab Fine grained cemented carbide with refined structure
US9005329B2 (en) 2007-06-01 2015-04-14 Sandvik Intellectual Property Ab Fine grained cemented carbide with refined structure
AT513422B1 (de) * 2012-09-13 2016-05-15 Tutec Gmbh Hexagonales WC-Pulver, Verfahren zu dessen Herstellung sowie Verwendung des Pulvers

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US20060029511A1 (en) 2006-02-09
DE602004008166T2 (de) 2008-04-30
KR20050013077A (ko) 2005-02-02
SE0302835D0 (sv) 2003-10-28
US20050025657A1 (en) 2005-02-03
EP1500713B1 (de) 2007-08-15
IL162686A0 (en) 2005-11-20
JP2005042201A (ja) 2005-02-17
ATE370257T1 (de) 2007-09-15
SE0302835L (sv) 2005-01-26
KR101202225B1 (ko) 2012-11-16
DE602004008166D1 (de) 2007-09-27
SE527173C2 (sv) 2006-01-17

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