±Ìt@CÌÐzÍÒ¨æÑ»Ì®@ÖÉÀÁÄø³êÄ¢Ü·B 9ÁW\ ³ÍÀ±ÌuyÑfÞÌJ­Ì»óÆ¡ãÌÛè \³ÍÀ±Åp¢çêé´dà
Tungsten Carbide Based Hardmetals Used for High Pressure Experimentac õ½
Kouhei WADA
Tungsten carbide based hardmetals have been used for the cylinders and anvils of high pressure apparatus, be­cause of their high hardness, compressive strength and Young's modulus. In this article, tungsten carbide based
hardmetals used for each high pressure apparatus are reviewed. In addition, newly developed ultra­fine grainedbinderless hardmetal TJS01 is introduced.
[tungsten carbide, hardmetal, anvil, stress­strain curve, uniaxial compression, mechanical properties]A.

Í¶ßÉíÞÌà®ÌY»¨ðSCRog(Co)CjbP
(Ni)ÈÇÌSnà®ðÞÆµÄp¢CÄ³Íð­¶·éZpÉ¨¯édvÈvfÌêÂ

µ½àðÌµC1925 NÉHÆ»³êÄÈ~CÉCÀSÉ³Íð­¶·é±ÆÌÅ«éHïÌÝv»ÌDê½@BIÁ«©çØíHïâÏÕpHïÆ»êÉÏ¦¤éÞ¿Ìgpª°çêéBÊíÆµÄL­p¢çêÄ¢éB´dàÌÅCYuðÝv·éÛÉHïÉ©©é³ÍÍCÞ¿Ìjó»^OXe(WC)ð Co àµ­Í Ni ðÄ­xCÜ½Í 0.2÷ÌivÐ¸Ýð¶¶éÌÍÜÆµÄÄµ½Þ¿ªÅà@BIÁ«ÉDêÄ¨ÌlÅè`³êé 0.2÷ÏÍÌ 8 öxðzèµÄèCêÊIÉ´dàÆÄÎêÄ¢éÞ¿ÍC{Þ¨èC»êÈãÌ³Í­¶ÅÍCuÌõ½ªZ­¿Ì±Æð¦·B

Èé¾¯ÅÈ­Cj¹ÌÉàÂÈªéÂ\«ªFig. 1 É WC_Co n´dàÌàgDáð¦·BZ¢ªªd¿(WC)C¢ªª(Co)Å

éB´dàÍC³kÌ@BIÁ«ªDêÄ¢é
½ßCÃ­©ç³ÍÀ±Åp¢çêÄ«½Bêû
ÅC³ÍÀ±ðsÁÄ¢éûXÌ½­ÍC´dàÍÀ±ðs¤½ßÌ¹ïÅÙÆñÇmçÈ¢Å

èC{Þ¿ÉÖµÄë¤B»±Å{eÅÍCÜ¸´dàÆÍÇÌlÈÞ¿èC2 Å\¬³êÄ¢é±qªU^ÌàÅ
é±Æªª©éBêÊIÉ´dàÍCFig. 2 ÌlÈHöÅ²èà@ðp¢Ä»ì³êéBÇÌHöài¿È´dàð¾é½ßÉåÈHöÅ

éªC±±ÅÍÁ

©CTªÆ»@ðÐî·éB»ÌãCî{IÈ´dÉe¿ªå«¢CfÞì»É¨¯éÅIHöÅàÌ@BIÁ«lð¦µC³ÍÀ±ÌÇÌuÄHöÉÂ¢Äðàðs¤BÉÇÌlÈ´dàªp¢çêÄ¢éÌ©ðÐî·Fig. 3 É Gurland(1954)Åñ³êÄ¢é WC_16 wt÷ Co g¬ÌYfÊÆ·xÌ[ñ³nóÔ}éBÅãÉCßNÒçªJ­µ½ WC_M2C ÄéÌ TJS01 ÉÖµÄÐî·éBðêÏXµ½}ð¦·[1]BêÊIÉ WC_Co n´dàÍCCo Ìto»·xæèãÌ 1300
C©

B.

ç 1500C Ì·xÅÄ³êéBÄÉdvÆÈéÌªàYfÊÅ éB@BIÁ«ªDê½S´dàÌTªCyÑ»@ÉÂ¢Ä´dàÍCüú\æÞa, ßa, àa °É®·é 9È´dàð¾é½ßÉÍCWC{g(Co C»

§257_0015 _Þì§`ìs½ò 36_1 ym_CX®ïÐ ZpJ­{ J­Z^[ Þ¿J­Materials Development Department Developed Center, Fuji Die Co., Ltd., 36_1 Hirasawa, Hadano­shi, Kanagawa 257_0015
Electronic address: wada.2733fujidie.co.jp

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Fig. 1. Optical image of a polished surface of WC_Co
hardmetal.
Fig. 3.

Phase relation of WC_16 wt÷ Co hardmetal.

bgÉC@BIÁ«lÌÎçÂ«ª½­­¶·é½ßC»iÌgpÉe¿ªÈ¢lÉCÊíÍÞí
É@BIÁ«lÌÇîðÝ¯Ä¨èCÀèµ½i¿ÆÈélÉÇðµÄ¢éBÜ½C´dàÌlÈ²èà@ðp¢ÄÄðs¤ÄÌÍCÄÌÌàÆOÌg¬·È­CÏêÉÄ·é±Æªïµ¢B´dàÅÍCÁÉYfÊÌàO·ª­¶·é±Æª½­C»ìðÉæÁÄÍ 20 mmFig. 2. The process of production for tungsten carbide
based hardmetals.

öxÌ÷úÅ ÁÄàCYfÊÌàO·ª 0.1÷Èã­¶µCáÊàÅÍSæÉüêé±ÆÅ·ç¢ïÆÈé±ÆàéB±ÌlÈg¬ÌàO·ª­¶·évöÍ½_©

éªCå^»iÉÈéÙÇCÜ½ WC Ì±xª÷±Càµ­Í\¢ fcc)Ì 2 àª¾çêélÉÄðs¤KÊÌàÙÇCÏêÉÄ·é±Æª¢ïÆÈéBvªéBàYfÊª¢Æ WC{g{Ci±Ì½ßCym_CXÅÍßÉÀÑÌÈ¢ÞíCCt[J[{ÆÄÎêéjÌ 3 CtÉá¢Æ WC{g{h(Co3W3C Ch ÆÄÎêéjÌ 3èàå«ÈÄÌÅêxÄ±ðs¤BÄãÌÌÌæÆÈèCWC Æ Co ÈOÌÙíªoÄÌÍØfµCàÜÅÏêÉÄªÅ«Ä¢éå«³Ì»iÌø«¢ªÁ½êC»Ì»iæ»µC@BIÁ«lÌåÈáºðN±·BÜ½C©ðCàYfÊCg¬C@BIÁ«lÌªèðs

WC{g ÌæÍáÊÌàÉÈéÙÇ·­Èé[2]BàYfÊÍC²Ì_»xâ¼xC¤±ÆÅmFµC»iÌi¿ÌÛØªÄÌKXµÍCi_fª³jÅeÕÉÏíééöxÅ«élÉµÄ©çóðó¯élÉµÄ¢éB±ÌlÉ´dàfÞð»ì·éãÅCÄHö
é½ßC

½ßCáÊàÌûªCÊàæèÆàYfÊÌÇÍñíÉdvÈÚÅ

àCÜ½÷±²ÉÈéÙÇÇªïµ¢BWC{´dàð»¢µÄ¢é[J[ÍCeÐ²ÌÇg ÌSæàÅÁÄàCàYfÊªÏ»·éÆ WC Ì±xÆÌ W ÌÅnÊàí¸©ÉÏ»·é½ßCd³CRÜÍÌ@BIÁ«làí¸©ÉÏ»·éBµ½ªÁÄC²bgâÄ³ÍmÈwgZp Vol. 28, No. 1 (2018)û@âÄû@ÉmEnEðÁÄ¨èC»êçà¥Ü¦ÄÞíIèðs¤ÌªÇ¢Åë¤B

±Ìt@CÌÐzÍÒ¨æÑ»Ì®@ÖÉÀÁÄø³êÄ¢Ü·B 11C.

´dàÌ@BIÁ«lÆ WC_Co n´dàð»ìµ½êCêÊIÉÍ´dàÍ±qªU^àÅé½ßC@BIÁ

WC_Co n´dàÌûªC@BIÁ«ÍDêÄ¢éB±êÍÌ³XÌÁ«lÌ·Æto»·é WC Ì±xÆÌÊÆíxª WC_Ni n´dàÌûªñ 70
C ­C»ÌÞÉË¶·éBWC Ì±xð÷±ÆµCÊðªÄ·xª­Èé½ßÉCWC ±qª±¬·µ¸ç·ÙÇCd³Íã¸·é[3]BÜ½C0.2÷ÏÍâ·¢½ßÅ«lÍd¿Å

Æ³k­xÍCWC Ì±xð÷±Æ·éCÜ½Í

éBÜ½CNi Í Co Æä×Ä«ª¢½ßÉC²¬ÉÃWÌðìèâ·­C

Êð­È­·éÙÇã¸µCO¦Í WC»ÌÃWÌªàgDàÉcèC­xáºðµ­±Ì±xÉË¶¹¸CÊÉË¶µC­È­Èé

Æà 1 ÂÌvöÅÙÇã¸·é[4]B±Ì½ßC³Í­¶ZpÌ­dàÍí·í³ðºÅñ¥«ÅBÉæèC­¶³Íª­ÈéÙÇC´dàÌd³C0.2÷ÏÍC³k­xCO¦Ì@BIÁH«ª¢ÌÁ¥ðÁÄ¨èCWC_Co n´dàªgpÅ«È¢ÁêÂ«Ågp³êé±Æª½«là¢Þ¿ªßçêCæè WC Ì±xª÷¢B±ÅáÊÌ´dàªp¢çêÄ«½B¡ÜÅÍPÈ WC ÆÌ´dàÉÂ¢Äq×Ä«½ªC´dàÍ WC ÆÈOÉCêûÅCWC Ì±xð÷±ÆµCÊð­È­·éÆCÞ¿ÌÕ«lÍáº·é[5]BÕ«ªáº·éÆC³ÍÀ±Åp¢éêÉCµ¢ªïµé[6]BêûÅCWC_Ni n´
èC³çÉÏ

TiC, VC, TaC, Mo2C, Cr3C2 ÌY»¨ª­ÊYÁ³êé±Æª éB±êçÌY»¨ÍCWC ±qÌ­Èé¾¯ÅÈ­CuÌACgÌâè©

±q¬·}§Càµ­ÍÌÅn­»ðÚIÆç¶¶éÎScÉã­Èé½ßCgpðÉæÁµÄYÁ³êCYÁµÄ¢È¢´dàæèà@BÄÍtÉõ½ªZ­ÈÁÄµÜ¤êªéBPIÁ«ªDêÄ¢é±Æª½¢[7]Bµ½ªÁÄC

É WC Ì±xª÷±ÅáÊÌàðg¦Î@BIÁ«ðüã³¹é½ßCßNÌ´dàÅÍCÇ¢í¯ÅÍÈ­CÀ±ðÉÞíIèðs¤ÌÙÆñÇÌÞíÅYÁ³êÄ¢éÆl¦ÄàÇ¢Å

Í±Ì½ßÅéBgp·éÞíÌIèÍ¡ÜÅÌë¤B

³ÍÀ±ÅÌgpÊ©çCo±¥ÅßÄ¢éêª½¢B»ÝCeí³Í­¶uÅp¢çêD.

³ÍÀ±Ép¢çêÄ¢é´dàÄ¢éÞíÉÖµÄÍCÌÅÚµ­q×éB
ÉÌíÞÉæé@BIÁ«lÌá¢ðq×éB¯ê WC ´¿ðp¢ÄCWC_Ni n´dà{ÚÅÍCxg^³Í­¶uÌV_CsXgCDIA ^³Í­¶uÌArgb

Fig. 4. The relations between mechanical properties and WC grain size and/or binder content of tungsten carbide based
hardmetals.

³ÍmÈwgZp Vol. 28, No. 1 (2018)12 ±Ìt@CÌÐzÍÒ¨æÑ»Ì®@ÖÉÀÁÄø³êÄ¢Ü·BvChbJ}[³Í­¶uâpEGWoàòÑUçÈ¢±ÆàIèÌRÅ³Í­¶uÌÎü^ArC»µÄìä^éB

³Í­¶uÌLéÆl¦çê[rbNArÅp¢çê

Éxg^ÌsXgCDIA ^ÌArgÄ¢é´dàÞ¿ðÐî·éBOÚÅàq×½bvÅp¢çêÄ¢éÞ¿ÉÖµÄÐî·éB{ÞªC±êçÌÞíIèÍ±ÅgpµÄ¸«CÊªÇ­C»ÝàgpµÄ¸¿ÉÍCbNEFd³ 90_93 HRA ÅCWC Ì±xª 0.5_1.5 nm Æ´÷±©ç±ÅCÊ¢Ä¢éÆÌo±¥©çÅª 5_13 wt÷Ì´dàªgp³êÄ¢éBV­ÜÅàßÉ³ÍÀèCæèÇ¢IðÌÂ

é±ÆðæÉfÁÄ¨­B_ÆÙÈèC©©éÍÌÙÆñÇª³kÍÆÈéxg^³Í­¶uÌV_Þ¿ÆµÄÍC{Þ¿ÍCÂ\ÈÀè³k­xÌDêéÞ¿ªIèbNEFd³ª 86_89 HRA ÅCWC Ì±xª1.5_4 nm ÜÅÌ±©çe±ÅCÊª 8_³êÄ¢éBêûÅC±êçÌuÅêÊIÉ­¶\«ª¼É³êé³ÍÍ 4_10 GPa Åé½ßCeT|[gC}bVuT|[gðÁ¦Ä±ÌöxÌ³15 wt÷ Co Ì éöx­xð¿CÕ«ÉDê½´dàªCÊí|ÞÉ³üCàµ­ÍÄüê³êÍª­¶Å«êÎ[ªÅèC´dàÌ­xÆÕÄp¢çêÄ¢éBV_Íø£ÍÅNbN«ÌoXðÆÁÄ±êçÌÞíÌIèª³ê½ªiWµÄjó·é±Æª½¢½ßC

Ì¾Æl¦çêéBéöx­xð¿CNbNªiWµÉ­¢Õ«ÌÞ¿ªIÅãÉCÎü^Arâìä^³Í­¶uÎê½½ß¾Æl¦çêéBÜ½Cªêj¹µÄ

Table 1.

Åp¢çêéL

[rbNAr¾ªC{Þ¿ÉTungsten carbide based hardmetals used for each high pressure apparatus.
Grain size of WC(nm)Binder content(wt÷)

Cylinder used for belt­type

1.5_4.0

8_15

D60, AG54, C60

Anvil used for belt­type

0.5_1.5

5_13

F09, F10, VD15, D20, VD45

1.0

13

TF05, TMS05, F08, TF06, F09, F10, MF10, VF12High pressure apparatus

Grade of Fuji Die Co., Ltd.

Anvil used for DIA­typeAnvil used for counter­typeAnvil used for Kawai­typeTable 2. Mechanical properties of tungsten carbide based hardmetals used for high pressure apparatus produced by Fuji Die
Co., Ltd.
GradeBinder
type

Rockwellhardness
(HRA)

TRS
(GPa)

Young'smodulus(GPa)

Compressive
strength(GPa)Fracture
toughness(MPa¥m1/2)

Thermalconductivity(W/m¥K)

TF05

Co

95.1

1.5

610

8.0

3.3

25

TMS05

Ni

95.0

3.1

610

8.0

4.2

20

F08

Co

93.5

3.9560

7.3

5.2

29

TF06

Co

93.5

3.5

610

7.3

5.1

50

F09

Co

93.0

4.4

540

7.2

6.5

42

F10

Co

92.5

3.8560

5.9

5.4

42

MF10

Ni

92.5

3.2

550

6.5

5.029VD15Co

92.0

3.2

620

5.5

6.4

89

VF12Co

91.5

3.6

560

5.4

7.6

72

D20Co

91.5

2.9

620

5.4

6.7

95

VD45

Co

90.0

3.5

540

4.9

9.7

78

D60

Co

88.0

3.4

520

4.3

15.0

82

AG54

Co

88.5

3.3

550

4.2

13.6

95

C60

Co

87.0

2.8

550

4.2

18.0

109

³ÍmÈwgZp Vol. 28, No. 1 (2018)

±Ìt@CÌÐzÍÒ¨æÑ»Ì®@ÖÉÀÁÄø³êÄ¢Ü·B 13

Table 3. Results of uniaxial compression, Young's modu­
lus, 0.2÷ proof strength and compressive strength.
Grade

Young'smodulus(GPa)0.2÷ proofstrength(GPa)Compressivestrength(GPa)
8.03

TF05

618

7.87

TF06

613

5.82

7.32

F08

568

5.96

7.32

F09

528

5.38

7.19

MF10564

4.80

6.46

AG54

554

3.21

4.20

ÌlÍJ^OlÅèCÛØlÅÍÈ¢±Æð²¹³¸«½¢B
Fig. 5. Typical true stress­true strain curves for tungsten
carbide based hardmetals.

ã\IÈÞíÌê²³kÀ±Éæè¾½^Í_^cÈü}ð Fig. 5 ÉCÜ½^Í_^cÈü©çZoµ½³kÌ@BIÁ«lð Table 3 É¦·B{f[^ÍCê Wada ç[9]ðøpµ½BV½ÈÍ³k­xÌÂ\ÈÀè¢Þ¿CbNEFd³ 91 HRA ÈãÅCWC Ì±xÍ 1 nm ÈºC³Í­¶uðJ­·éêÌÝvÉ{Á«lðp¢Ä¢½¾¯êÎK¢ÅéBÊÍ 13 wt÷ÈºÌ´dàªp¢çêÄ¢éBÎü^ArÍ`óÉæÁÄlXÈÞíªgp³
êÄ¢éªCLE.

WC_M2C ÄÌ TJS01[rbNArÍ¨¨æ»­¶³ÍÉæègp·éÞíªÜÁÄ¨èCñ
20 GPa ÜÅÌ³ÍÅÍCbNEFd³ª 93_94 HRA öxÌ´dàªgp³êC»êÈãÌ³

ìä^³Í­¶uÌåeÊvXðp¢½
À±É¨¢ÄC´dàðp¢Ä­¶Å«é³ÍÍÍÅÍC»êæèàd¢Þ¿ªgp³êéBÈ¨C30 GPa öxÉÀçêÄ¨èC»êÈãÌ³Í­¶ðs¤½ßÉÍ¿ÈÄ_ChðArêÊIÉ´dàðp¢Ä­¶Â\ÈÅå³ÍÍñÞ¿ÆµÄp¢éµ©È©Á½Bµ½ªÁÄC

30 GPa Æ¢íêÄ¢éB±êÜÅq×Ä«½±ÆÆÀÛÉ³Í­¶u30 GPa ÈãÌ³ÍðºÅÌÀ±ÍZpIÉïµ­C³çÉïpªåÉ©©é±ÆªâèÅ ÁÅgp³êÄ¢éym_CX»´dàÞíÌã\½BÜ½CÄ_Chðp¢ÄÍïµ¢À±Cá ð Table 1 C » ê ç Ì Þ í Ì @ B I Á « l ðá¦Î 30 GPa ÈãÌ³ÍðºÅÌ 2000
C ÈãTable 2 É¦·BÙÆñÇÌÞíÌÍ Co ÅéªCMF10 Æ TMS05 ÌÝ Ni Å èC±êç 2ïÅÞíÍC³ÍðºÅÌ¥«ªèÀ±â«qñ

Ì·À±ÍCåeÊvXðp¢½À±ÅÍ¢Á½B

Êª 1 wt÷ÈºÌ´dàÍC[oCÜÀ±Åp¢çêÄ¢éB{@BIÁ«lð¼Ð_XÄÌCàµ­ÍoC_XÄÌiÈº[J[Ìd¿Þ¿Æär·éêC[J[ÉoC_XÄÌÆLqjÆÄÎêÄ¢éB±êªèû@âÝè·élÌîªÙÈé½ßCÓªçÌÄÌÍåÆµÄ¾Ê«ªv³êéprCKvÅéBá¦ÎCjóÕ«lÍªèû@Ægp·é®ÉæÁÄClÉå«È·ª¶¶éBym_CXÌêÍCjóÕ«lÍrbJ[X³­@ðp¢á¦ÎñÊKXY¬`pà^Þ¿ÆµÄgp³êÄ¢éBoC_XÄÌÍCd­CO¦ª¢ÁÄCV´Ì®[8]ðgpµÄZoµÄ¢é½ßC¼¥ðÁÄ¢é½ßC¡ÜÅ½x©±IÉ³ÍÐÌ¦µÄ¢élæèàêÊIÉ¬³Èlð¦·B­¶À±Ågp³ê½±ÆÍÁ½Bµ©µC­xµ½ªÁÄC¼Ð[J[ÆÌÁ«lÌärÍQls«Ì½ßÉCÀ±Éu[AEg·éÇ¢öx¾Æl¦Ä¢½¾¢½ûªÇ¢BÜ½C±êçÊª¾çê¸CêÊIÉ³ÍÀ±Åp¢çêÄ«³ÍmÈwgZp Vol. 28, No. 1 (2018)14 ±Ìt@CÌÐzÍÒ¨æÑ»Ì®@ÖÉÀÁÄø³êÄ¢Ü·B

Fig. 7. Typical true stress­true strain curves for TJS01
and other hardmetals.
Fig. 6. SEM images of a surface of JF03 and TJS01
etched with 10 wt÷ KOH{10 wt÷ K3Fe(CN)6 solution(Murakami's reagent).

½´dàÍCÊª 3 wt÷ÈãÌàÅ
Á½BoC_XÄÌÌ­xªá¢´öÍCSæª©Èè·­C³çÉÄ·xà 1500
C©
ç 1800C Æ©Èè¢½ßCÙíÌÍoâ WCÌÙí¬·ªN±èâ·­CSÈgDðÛÁ½ÜÜÌÄªñíÉïµ¢½ßÉCêÊIÉzbgv

Table 4. Mechanical properties of ultra­fine grained bin­derless hardmetal TJS01.
GradeVickers
hardnessat 294 N(GPa)TRS(GPa)

Young'smodulus(GPa)Compressive
strength(GPa)

TJS01

27.5

2.6665

8.0JF0321.91.8705TF05

24.1

2.5618

4.7
8.0

F08

19.6

4.45687.3

X@âpXÊdÁ³Ä@Ìû@Åì»³êÄ¢é½ßÅéB·Èí¿C±êçÌÄû@Åì»µ½êCYfÊâ WC ±xÌàO·ªå«êÄ¢é´dàÌÅÅà÷±qÅèCrb­CÄ«à«¢½ßÉ­xªá¢BJ[Xd³à 27 GPa ÈãÆdxÅ

Á½BFig.

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Á½ 30 GPa ÈãÌ³ÍÀ±É¨¢ÄCLpÈÞ¿ÅéÆl¦çêéB[1] J. Gurland: J. Metals, 6, 285, 1327 (1954).
[2] éØõ: ú{à®wïïñ, 11, 125 (1972).
[3] J. Gurland: Trans. Met. Soc. AIME, 227, 1146(1963).
[4] A. Hara, T. Ikeda: Trans. JIM, 13, 128 (1972).
[5] J.L. Chermant, F. Osterstock: J. Mater. Sci., 11,1939 (1976).
[6] éØõ, cC, r_V: ´Ì¨æÑ²èà, 42, 1345 (1995).
[7] ÑG¢, ÆNé, éØõ: ´Ì¨æÑ²èà, 19, 67 (1972).
[8] V´©ê: Z~bNX, 20, 12 (1985).
[9] K. Wada, T. Yagi, H. Gotou, R. Iizuka, M.

³ÍmÈwgZp Vol. 28, No. 1 (2018)16 ±Ìt@CÌÐzÍÒ¨æÑ»Ì®@ÖÉÀÁÄø³êÄ¢Ü·B

Kawakami, K. Kitamura, K. Hayashi: HighPressure Res., 35, 263 (2015).
[10] T. Kunimoto, T. Irifune, Y. Tange, K. Wada:High Pressure Res., 36, 97 (2016).
[11] T. Ishii, D. Yamazaki, N. Tsujino, X. Fang, Z.
Liu, T. Kawazoe, T. Yamamoto, D. Druzhbin, L.

³ÍmÈwgZp Vol. 28, No. 1 (2018)

Wang, Y. Higo, Y. Tange, T. Yoshino, T. Katsura:High Pressure Res., 37, 507 (2017).
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