JP2021001094A - Silicon nitride sintered body and abrasion resistant member using it - Google Patents
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- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 229910052581 Si3N4 Inorganic materials 0.000 title claims abstract description 93
- 238000005299 abrasion Methods 0.000 title abstract 2
- 239000002245 particle Substances 0.000 claims abstract description 75
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 27
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 26
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 24
- 239000013078 crystal Substances 0.000 claims abstract description 19
- 150000004767 nitrides Chemical class 0.000 claims description 11
- 150000001247 metal acetylides Chemical class 0.000 claims description 8
- 150000004678 hydrides Chemical class 0.000 claims description 3
- 238000005245 sintering Methods 0.000 description 41
- 239000010936 titanium Substances 0.000 description 29
- 239000000843 powder Substances 0.000 description 26
- 238000000034 method Methods 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 13
- 230000003746 surface roughness Effects 0.000 description 13
- 239000006185 dispersion Substances 0.000 description 10
- 239000002002 slurry Substances 0.000 description 10
- 238000005096 rolling process Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 229910052761 rare earth metal Inorganic materials 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 238000005238 degreasing Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000013001 point bending Methods 0.000 description 4
- 238000005498 polishing Methods 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 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 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 238000007517 polishing process Methods 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052692 Dysprosium Inorganic materials 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229910052769 Ytterbium Inorganic materials 0.000 description 2
- 229910026551 ZrC Inorganic materials 0.000 description 2
- OTCHGXYCWNXDOA-UHFFFAOYSA-N [C].[Zr] Chemical compound [C].[Zr] OTCHGXYCWNXDOA-UHFFFAOYSA-N 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 229910052790 beryllium Inorganic materials 0.000 description 2
- 230000000740 bleeding effect Effects 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 2
- WHJFNYXPKGDKBB-UHFFFAOYSA-N hafnium;methane Chemical compound C.[Hf] WHJFNYXPKGDKBB-UHFFFAOYSA-N 0.000 description 2
- 230000002706 hydrostatic effect Effects 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- -1 titanium hydride Chemical compound 0.000 description 2
- 229910000048 titanium hydride Inorganic materials 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 2
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 2
- 229910000568 zirconium hydride Inorganic materials 0.000 description 2
- ZVWKZXLXHLZXLS-UHFFFAOYSA-N zirconium nitride Chemical compound [Zr]#N ZVWKZXLXHLZXLS-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052773 Promethium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 239000006061 abrasive grain Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000004520 agglutination Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229910000449 hafnium oxide Inorganic materials 0.000 description 1
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 1
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 229910052705 radium Inorganic materials 0.000 description 1
- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium atom Chemical compound [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 239000010723 turbine oil Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- QSGNKXDSTRDWKA-UHFFFAOYSA-N zirconium dihydride Chemical compound [ZrH2] QSGNKXDSTRDWKA-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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Abstract
Description
実施形態は、窒化珪素焼結体およびそれを用いた耐摩耗性部材に関する。 The embodiment relates to a silicon nitride sintered body and a wear resistant member using the same.
窒化珪素を主成分とするセラミックス焼結体は、優れた耐熱性を示し、かつ熱膨張係数が小さいため、耐熱衝撃性にも優れる等の諸特性を有することから、従来の耐熱合金に代わる高温構造用材料として、エンジン部品、製鋼用機械部品等への応用が進んでいる。また、耐摩耗性にも優れていることから、転動部材や切削工具としての実用化も図られている。 Ceramic sintered bodies containing silicon nitride as the main component exhibit excellent heat resistance and have various properties such as excellent thermal impact resistance due to their small coefficient of thermal expansion. Therefore, they have a high temperature that replaces conventional heat-resistant alloys. As a structural material, its application to engine parts, machine parts for steelmaking, etc. is advancing. In addition, since it has excellent wear resistance, it has been put into practical use as a rolling member and a cutting tool.
特開２０１７−７５０７３号公報（特許文献１）には、焼結助剤として、Ａｌ２Ｏ３（酸化アルミニウム）、ＡｌＮ（窒化アルミニウム）、ＴｉＯ２（酸化チタン）、Ｂ（ホウ素）、Ｃ（炭素）、Ｍｏ（モリブデン）、Ｗ（タングステン）、Ｃｕ（銅）、Ｎｉ（ニッケル）等を原料粉末に所定量添加して焼結性を改善し、緻密で高強度な窒化珪素焼結体を得ている。一方で、近年では製品の小型化高性能化により、摺動部材に負荷がかかり表面組織に微細な脱粒が発生するという問題が起こっている。
窒化珪素摺動部材に対する耐脱粒性を改善するため、特許第５８２５９６２号公報（特許文献２）には、焼結助剤としてジルコニア（ＺｒＯ２）、イットリア（Ｙ２Ｏ３）、セリア（ＣｅＯ２）、マグネシア（ＭｇＯ）、カルシア（ＣａＯ）を焼結助剤とした窒化珪素焼結体が開発されている。しかしながら、製品性能向上によりセラミックス部材に対する品質要求も上がり、ハイエンドな使用環境ではセラミックスに掛かる負荷が大きくなっているため、従来の品質特性では十分であるとは言えなくなっている。
Japanese Patent Application Laid-Open No. 2017-75073 (Patent Document 1) describes Al2O3 (aluminum oxide), AlN (aluminum nitride), TiO2 (tungsten oxide), B (boron), C (carbon), and Mo as sintering aids. (Molybdenum), W (tungsten), Cu (copper), Ni (nickel) and the like are added in a predetermined amount to the raw material powder to improve the sinterability, and a dense and high-strength aluminum nitride sintered body is obtained. On the other hand, in recent years, due to the miniaturization and high performance of products, there has been a problem that a load is applied to the sliding member and fine shedding occurs on the surface structure.
In order to improve the degranulation resistance to the silicon nitride sliding member, Japanese Patent No. 5825962 (Patent Document 2) states that zirconia (ZrO2), yttria (Y2O3), ceria (CeO2), and magnesia (MgO) are used as sintering aids. ), A silicon nitride sintered body using calcia (CaO) as a sintering aid has been developed. However, as the product performance is improved, the quality requirements for ceramic members are also increased, and the load on the ceramics is increased in a high-end usage environment, so that the conventional quality characteristics cannot be said to be sufficient.
近年、窒化珪素焼結体は、エンジン部品、機械部品、ベアリングボール、切削工具など様々な耐摩耗性部材に使用されている。窒化珪素焼結体は、軸受鋼（ＳＵＪ２）などの金属部材と比べてはるかに耐久性に優れることから、各種耐摩耗性部材において長期信頼性を得ている。このため、長期間メンテナンスフリーをも実現している。
近年製品の小型化や高性能化に伴い、従来よりも厳しい品質特性が求められるようになってきている。例えば窒化珪素が使用されたベアリングは、宇宙・航空・自動車・鉄道・工作機器・家電など、より小型で高速な回転とともにメンテナンスフリーが要求されている。このため窒化珪素部品に掛かる負荷は大きくなっており、過酷な使用環境下における耐脱粒性に関しては必ずしも十分ではなかった。
In recent years, silicon nitride sintered bodies have been used for various wear-resistant members such as engine parts, mechanical parts, bearing balls, and cutting tools. Since the silicon nitride sintered body is far more durable than metal members such as bearing steel (SUJ2), long-term reliability is obtained in various wear-resistant members. For this reason, maintenance-free operation is also realized for a long period of time.
In recent years, with the miniaturization and higher performance of products, stricter quality characteristics than before have been required. For example, bearings made of silicon nitride are required to be smaller and faster to rotate and maintenance-free for space, aviation, automobiles, railways, machine tools, home appliances, etc. For this reason, the load applied to the silicon nitride component is large, and the shedding resistance under a harsh usage environment is not always sufficient.
実施形態にかかる窒化珪素焼結体は、このような問題を解決するためのものであり、窒化珪素結晶粒子と粒界相を具備する窒化珪素焼結体の任意の５０μｍ２以上の断面を撮影したとき、チタン（Ｔｉ）、ジルコニウム（Ｚｒ）、ハフニウム（Ｈｆ）から選ばれる１種以上の４Ａ族元素が５０ｗｔ％以上含まれる粒子が複数存在し、かつそれらの粒子同士の粒子間最近接距離が１μｍ以上である組み合わせが５０％を超えることを特徴とする。
The silicon nitride sintered body according to the embodiment is for solving such a problem, and an arbitrary cross section of 50
実施形態にかかる窒化珪素焼結体は、Ｔｉ、Ｚｒ、Ｈｆから選ばれる１種以上の４Ａ族元素粒子の粒子同士の粒子中心最近接距離を制御している。これにより窒化珪素組織の耐脱粒性を向上することを可能とする。そのため、実施形態の窒化珪素焼結体を用いた耐摩耗性部材は、繰り返し疲労負荷に対する長期間信頼性を維持することができる。 The silicon nitride sintered body according to the embodiment controls the closest contact distance between the particles of one or more Group 4A element particles selected from Ti, Zr, and Hf. This makes it possible to improve the shedding resistance of the silicon nitride structure. Therefore, the wear-resistant member using the silicon nitride sintered body of the embodiment can maintain reliability for a long period of time against repeated fatigue loads.
実施形態にかかる窒化珪素焼結体は、窒化珪素結晶粒子と粒界相を具備する窒化珪素焼結体の任意の断面を撮影したとき、単位面積５０μｍ２あたり、Ｔｉ、Ｚｒ、Ｈｆから選ばれる１種以上の４Ａ族元素が５０ｗｔ％以上含まれる粒子が複数存在し、かつそれらの粒子同士の粒子中心間最近接距離が１μｍ以上である組み合わせが５０％を超えることを特徴とするものである。
窒化珪素焼結体は、主相となる窒化珪素結晶粒子と副相である粒界相を具備している。粒界相は、焼結助剤が焼結工程において焼結同士または焼結助剤と窒化珪素（不純物酸素含む）が反応した化合物から主に形成されている。燒結助剤は焼結性を制御するために添加されており、粒界相は窒化珪素結晶粒子同士の隙間（粒界）に形成される。粒界相により窒化珪素結晶粒子同士の結合力を強化している。
The silicon nitride sintered body according to the embodiment is selected from Ti, Zr, and Hf per unit area of 50 μm2 when an arbitrary cross section of the silicon nitride sintered body having the silicon nitride crystal particles and the grain boundary phase is photographed. It is characterized in that there are a plurality of particles containing 50 wt% or more of Group 4A elements of species or more, and the number of combinations in which the closest contact distance between the particle centers of these particles is 1 μm or more exceeds 50%.
The silicon nitride sintered body includes silicon nitride crystal particles as the main phase and grain boundary phases as subphases. The grain boundary phase is mainly formed from a compound in which the sintering aid reacts with each other in the sintering step or with the sintering aid and silicon nitride (including impurity oxygen). The sinter aid is added to control the sinterability, and the grain boundary phase is formed in the gaps (grain boundaries) between the silicon nitride crystal grains. The grain boundary phase strengthens the bonding force between silicon nitride crystal particles.
窒化珪素結晶粒子と粒界相を比較したとき、粒界相は窒化珪素結晶粒子よりも脆く選択的に脱粒が起こる。特に、酸化物由来のアモルファス相からなる粒界相は強度が弱く、研磨加工時には優先的に脱粒して加工起点となることが分かっている。
窒化珪素焼結体全体の耐脱粒性を向上させるためには、粒界相を強化して窒化珪素の状態に近づけること、および脱粒の起点となる粒界相を一ヵ所に集中させないことが有効である。粒界相を強化して窒化珪素に近づけるためには、Ｔｉ、Ｚｒ、Ｈｆの４Ａ族を粒界相に配置することが効果的である。これは、４Ａ族元素の窒化物や炭化物などの化合物は融点が高く耐熱性において優れていること、および硬度が高いことにより粒界相を補強して窒化珪素の状態に近づけることができるためである。
When the grain boundary phase is compared with the silicon nitride crystal particles, the grain boundary phase is more brittle than the silicon nitride crystal particles and selective degranulation occurs. In particular, it is known that the grain boundary phase composed of an oxide-derived amorphous phase has low strength and preferentially threshes during polishing to serve as a starting point for processing.
In order to improve the shedding resistance of the entire silicon nitride sintered body, it is effective to strengthen the grain boundary phase to bring it closer to the state of silicon nitride and not to concentrate the grain boundary phase, which is the starting point of shedding, in one place. Is. In order to strengthen the grain boundary phase and bring it closer to silicon nitride, it is effective to arrange Group 4A of Ti, Zr, and Hf in the grain boundary phase. This is because compounds such as nitrides and carbides of Group 4A elements have a high melting point and excellent heat resistance, and the high hardness makes it possible to reinforce the grain boundary phase and bring it closer to the state of silicon nitride. is there.
粒界相粒子に含まれるＴｉ、Ｚｒ、Ｈｆから選ばれる１種以上の４Ａ族元素の割合を５０ｗｔ％以上としている。これは４Ａ族元素の割合を５０ｗｔ％未満にすると、粒界相を十分に強化できない可能性があるためである。
また、単位面積５０μｍ２といった微小領域において対象とする粒子同士の粒子間距離が１μｍ以上である組み合わせを５０％以上の範囲にしている。粒子同士の組み合わせが５０％未満では、脱粒する可能性のある組み合わせが多くなりすぎて窒化珪素焼結体の耐脱粒性が低下する。また、組み合わせは上限を定めていないが、１００％であれば脱粒の可能性が少なくなり理想的に粒界相が分布しているといえる。そのため、対象とする粒子同士の粒子間距離が１μｍ以上である組み合わせは５０％以上であり、好ましくは６０％以上である。
The ratio of one or more Group 4A elements selected from Ti, Zr, and Hf contained in the grain boundary phase particles is 50 wt% or more. This is because if the proportion of Group 4A elements is less than 50 wt%, the grain boundary phase may not be sufficiently strengthened.
Further, in a minute region such as a unit area of 50 μm2, the combination in which the interparticle distance between the target particles is 1 μm or more is in the range of 50% or more. If the combination of particles is less than 50%, the number of combinations that may shed is too large, and the shedding resistance of the silicon nitride sintered body is lowered. Further, although the upper limit of the combination is not set, if it is 100%, the possibility of shedding is reduced and it can be said that the grain boundary phase is ideally distributed. Therefore, the combination in which the inter-particle distance between the target particles is 1 μm or more is 50% or more, preferably 60% or more.
なお、粒子に含まれるＴｉ、Ｚｒ、Ｈｆから選ばれる１種以上の４Ａ族元素の割合の測定方法は次の通りである。まず、窒化珪素焼結体の任意の断面を得る。この断面を表面粗さＲａが１μｍ以下の鏡面加工を施す。得られた鏡面をＴＥＭ（Ｔｒａｎｓｍｉｓｓｉｏｎ Ｅｌｅｃｔｒｏｎ Ｍｉｃｒｏｓｃｏｐｅ：透過電子顕微鏡）にて１０００倍以上の倍率で画像観察する。５０μｍ２の領域の設定では、その形状を限定するものではないが、恣意的な観察を避けるため正方形に近い形を設定することが好ましい。例えば、７．１μｍ×７．１μｍ（＝５０．４１μｍ２）、や７μｍ×８μｍ（＝５６μｍ２）などが挙げられる。ＴＥＭ観察において、Ｔｉ、Ｚｒ、Ｈｆから選ばれる１種以上の４Ａ族元素が観察された場合は、ｗｔ％を確認して対象粒子が５０ｗｔ％以上であることを確認する。
なお、単位面積５０μｍ２以上にならない場合は、隣接する箇所を複数撮影し繋ぎ合わせることにより合計で単位面積５０μｍ２以上にしてもよいものとする。
図２に窒化珪素焼結体のＴｉ分布観察の一例を示す。撮影面積は９２．８μｍ２（＝１１．２５μｍ×８．２５μｍ）であり、Ｔｉが５０ｗｔ％以上の粒子が６個観察される。６個の粒子同士の組み合わせは１５ヵ所あり、このうち粒子同士の粒子間距離が１μｍ以上である組み合わせは１４ヵ所（１μｍ以下の組み合わせは１ヵ所）なので、対象とする粒子同士の粒子間距離が１μｍ以上である組み合わせは９３．３％である。
The method for measuring the ratio of one or more Group 4A elements selected from Ti, Zr, and Hf contained in the particles is as follows. First, an arbitrary cross section of the silicon nitride sintered body is obtained. This cross section is mirror-finished with a surface roughness Ra of 1 μm or less. The obtained mirror surface is image-observed with a TEM (Transmission Electron Microscope) at a magnification of 1000 times or more. The setting of the region of 50
If the unit area does not exceed 50 μm2, the total unit area may be 50 μm2 or more by photographing a plurality of adjacent locations and connecting them together.
FIG. 2 shows an example of observing the Ti distribution of the silicon nitride sintered body. The photographing area is 92.8 μm 2 (= 11.25 μm × 8.25 μm), and six particles having a Ti content of 50 wt% or more are observed. There are 15 combinations of 6 particles, of which 14 are combinations where the inter-particle distance between particles is 1 μm or more (1 location is a combination of 1 μm or less), so the inter-particle distance between target particles is The number of combinations that are 1 μm or more is 93.3%.
粒界相はＴｉ、Ｚｒ、Ｈｆから選ばれる１種以上の４Ａ族元素を含む粒子が存在することが好ましい。４Ａ族元素を含む粒子は、４Ａ族元素の酸化物、窒化物、水素化物、炭化物のいずれかの化合物単体であることが好ましい。化合物単体とは、Ｔｉの場合、ＴｉＯ２（酸化チタン）、ＴｉＮ（窒化チタン）、ＴｉＨ２（水素化チタン）、ＴｉＣ（炭化チタン）のいずれか１種以上となる。Ｚｒの場合は、ＺｒＯ２（酸化ジルコニウム）、ＺｒＮ（窒化ジルコニウム）、ＺｒＨ２（水素化ジルコニウム）、ＺｒＣ（炭化ジルコニウム）のいずれか１種以上となる。また、Ｈｆの場合、ＨｆＯ２（酸化ハフニウム）、ＨｆＮ（窒化ハフニウム）、ＨｆＨ２（水素化ハフニウム）、ＨｆＣ（炭化ハフニウム）のいずれか１種以上となる。これらの中では４Ａ族元素の窒化物または炭化物が好ましい。特に、ＴｉＮまたはＴｉＣが好ましい。 As the grain boundary phase, it is preferable that particles containing one or more Group 4A elements selected from Ti, Zr, and Hf are present. The particles containing the Group 4A element are preferably a simple compound of any of the oxides, nitrides, hydrides, and carbides of the Group 4A element. In the case of Ti, the compound simple substance is any one or more of TiO2 (titanium oxide), TiN (titanium nitride), TiH2 (titanium hydride), and TiC (titanium carbide). In the case of Zr, it is one or more of ZrO2 (zirconium oxide), ZrN (zirconium nitride), ZrH2 (zirconium hydride), and ZrC (zirconium carbide). Further, in the case of Hf, it is one or more of HfO2 (hafnium oxide), HfN (hafnium nitride), HfH2 (hafnium hydrogenated), and HfC (hafnium carbide). Of these, nitrides or carbides of Group 4A elements are preferred. In particular, TiN or TiC is preferable.
Ｔｉ、Ｚｒ、Ｈｆから選ばれる１種以上の４Ａ族元素を含む粒子は、焼結助剤として化合物単体として添加したものであっても良いし、焼結工程で化合物単体に変化したものであっても良い。
また、Ｔｉ、Ｚｒ、Ｈｆから選ばれる１種以上の４Ａ族元素を含む粒子は化合物単体の結晶粒子となる。なお、結集粒子となっているか否かはＴＥＭ観察時に定性分析にて判断できる。
また、Ｔｉ、Ｚｒ、Ｈｆから選ばれる１種以上の４Ａ族元素を含む粒子は、Ｓｉ元素および他の添加物として加えられた場合に存在する２Ａ族元素と固溶していないことが好ましい。Ｓｉ元素および２Ａ族元素と固溶すると、４Ａ族元素の化合物単体が、４Ａ族元素とＳｉ元素または２Ａ族元素の複合化合物となる。複合化合物は化合物単体と比べて耐脱粒性が低下する。また、本願発明とは直接的には関係はないが、耐薬品性についても低下する可能性がある。このため、Ｓｉ元素または２Ａ族元素と複合化合物を形成しない化合物単体が好ましい。前述のＴｉＮやＴｉＣは複合化合物を形成し難いため好ましい。
図３にチタン部分の元素分析の一例を示す。ＴＥＭ観察によるＴｉ、窒素（Ｎ）、炭素（Ｃ）の元素分析写真であり、窒素が検出されることから、Ｔｉ部分は窒化物であるといえる。
The particles containing one or more Group 4A elements selected from Ti, Zr, and Hf may be added as a simple substance as a sintering aid, or may be changed to a simple substance in the sintering step. You may.
Further, the particles containing one or more Group 4A elements selected from Ti, Zr, and Hf are crystal particles of the compound alone. Whether or not the particles are aggregated particles can be determined by qualitative analysis during TEM observation.
Further, it is preferable that the particles containing one or more Group 4A elements selected from Ti, Zr, and Hf are not solid-solved with the Si element and the Group 2A elements present when added as other additives. When solidly dissolved with the Si element and the 2A group element, the compound simple substance of the 4A group element becomes a composite compound of the 4A group element and the Si element or the 2A group element. The composite compound has lower shedding resistance than the compound alone. Moreover, although it is not directly related to the present invention, the chemical resistance may be lowered. Therefore, a simple compound that does not form a complex compound with a Si element or a group 2A element is preferable. The above-mentioned TiN and TiC are preferable because it is difficult to form a complex compound.
FIG. 3 shows an example of elemental analysis of the titanium portion. It is an elemental analysis photograph of Ti, nitrogen (N), and carbon (C) by TEM observation, and since nitrogen is detected, it can be said that the Ti portion is a nitride.
Ｔｉ、Ｚｒ、Ｈｆから選ばれる１種以上の４Ａ族元素を含む粒子は長径が０．３μｍ以上であることが好ましい。長径が０．３μｍ未満であると結晶粒子が小さくなりすぎて外部から加えられた力により脱粒しやすくなる。また、長径は２μｍ以下であることが好ましい。長径が２μｍを超えると、結晶粒子端部が折れやすくなり、折れた部分が脱粒しやすくなる。このため、Ｔｉ、Ｚｒ、Ｈｆから選ばれる１種以上の４Ａ族元素を含む粒子の長径は０．３μｍ以上および２μｍ以下であることが好ましい。
また、窒化珪素焼結体の任意の断面組織を撮影したとき、単位面積５０μｍ２あたり、Ｔｉ、Ｚｒ、Ｈｆから選ばれる１種以上の４Ａ族元素を含む粒子が２個以上存在することが好ましい。単位面積あたりの粒子の個数が０〜１個の場合、４Ａ族元素を含む粒子が存在しない領域が大きくなり、耐摩耗性に悪影響が出る可能性がある。
このため、Ｔｉ、Ｚｒ、Ｈｆから選ばれる１種以上の４Ａ族元素を含む粒子は、粒子に含まれるＴｉ、Ｚｒ、Ｈｆから選ばれる１種以上の４Ａ族元素の割合を５０ｗｔ％以上であること、長径が０．３μｍ〜２μｍであること、単位面積５０μｍ2あたり２個以上存在すること、をすべて満たすことが最も好ましい。
The particles containing one or more Group 4A elements selected from Ti, Zr, and Hf preferably have a major axis of 0.3 μm or more. If the major axis is less than 0.3 μm, the crystal particles become too small and easily shed by the force applied from the outside. Further, the major axis is preferably 2 μm or less. When the major axis exceeds 2 μm, the end portion of the crystal particle is easily broken, and the broken portion is easily shed. Therefore, the major axis of the particles containing one or more Group 4A elements selected from Ti, Zr, and Hf is preferably 0.3 μm or more and 2 μm or less.
Further, when an arbitrary cross-sectional structure of the silicon nitride sintered body is photographed, it is preferable that two or more particles containing one or more Group 4A elements selected from Ti, Zr, and Hf are present per 50 μm2 unit area. When the number of particles per unit area is 0 to 1, the region where particles containing Group 4A elements do not exist becomes large, and the wear resistance may be adversely affected.
Therefore, the particle containing one or more Group 4A elements selected from Ti, Zr, and Hf has a ratio of one or more Group 4A elements selected from Ti, Zr, and Hf contained in the particles of 50 wt% or more. It is most preferable to satisfy all of the above, that the major axis is 0.3 μm to 2 μm, and that there are two or more per unit area of 50 μm2.
また、前記窒化珪素焼結体は、上記４Ａ族以外に、２Ａ族元素、５Ａ族元素、６Ａ族元素、３Ｂ族元素、希土類元素を含むことが好ましい。２Ａ族元素、５Ａ族元素、６Ａ族元素、３Ｂ族元素、希土類元素は焼結工程にて反応して粒界相を形成するための焼結助剤として使用されるものである。 Further, the silicon nitride sintered body preferably contains a group 2A element, a group 5A element, a group 6A element, a group 3B element, and a rare earth element in addition to the above group 4A. Group 2A elements, Group 5A elements, Group 6A elements, Group 3B elements, and rare earth elements are used as sintering aids for reacting in the sintering step to form a grain boundary phase.
２Ａ族元素を添加する際は、Ｂｅ（ベリリウム）、Ｍｇ（マグネシウム）、Ｃａ（カルシウム）、Ｓｒ（ストロンチウム）、Ｂａ（バリウム）、Ｒａ（ラジウム）のいずれか、可能ならばＢｅ、Ｍｇ、Ｃａ、Ｓｒのいずれか１種類以上から選択するのが望ましい。また、５Ａ族元素を添加する際は、Ｖ（バナジウム）、Ｎｂ（ニオブ）、Ｔａ（タンタル）、６Ａ族元素を添加する際は、Ｃｒ（クロム）、Ｍｏ（モリブデン）、Ｗ（タングステン）から選択するのが望ましい。３Ｂ族元素は、Ｂ（ホウ素）、Ａｌ（アルミニウム）から選択するのが望ましい。焼結助剤として２Ａ族元素成分、５Ａ族元素成分、６Ａ族元素成分、３Ｂ族元素成分を添加する際は、酸化物、炭化物、窒化物のいずれか１種として添加することが望ましい。 When adding a group 2A element, any of Be (beryllium), Mg (magnesium), Ca (calcium), Sr (strontium), Ba (barium), Ra (radium), and if possible, Be, Mg, Ca. , Sr, it is desirable to select from one or more of them. When adding Group 5A elements, use V (vanadium), Nb (niobium), Ta (tantalum), and when adding Group 6A elements, use Cr (chromium), Mo (molybdenum), and W (tungsten). It is desirable to choose. The Group 3B element is preferably selected from B (boron) and Al (aluminum). When the group 2A element component, the group 5A element component, the group 6A element component, and the group 3B element component are added as the sintering aid, it is desirable to add them as one of oxides, carbides, and nitrides.
また、希土類元素を添加する場合はＹ（イットリウム）、Ｌａ（ランタン）、Ｃｅ（セリウム）、Ｐｒ（プラセオジム）、Ｎｄ（ネオジウム）、Ｐｍ（プロメチウム）、Ｓｍ（サマリウム）、Ｅｕ（ユーロピウム）、Ｇｄ（ガドリウム）、Ｔｂ（テルビウム）、Ｄｙ（ジスプロシウム）、Ｈｏ（ホルミウム）、Ｅｒ（エルビウム）、Ｔｍ（ツリウム）、Ｙｂ（イッテルビウム）、Ｌｕ（ルテチウム）のいずれから１種類以上を選択するのが望ましい。窒化珪素の焼結において、希土類元素を添加した場合、焼結性が向上し、窒化珪素結晶粒子のアスペクト比が向上、結果として強度特性、耐摩耗性に非常に優れた焼結体を得ることができる。 When adding rare earth elements, Y (ytterbium), La (lantern), Ce (cerium), Pr (placeodymium), Nd (neodymium), Pm (promethium), Sm (samarium), Eu (europyum), Gd It is desirable to select one or more of (gadolinium), Tb (dysprosium), Dy (dysprosium), Ho (holmium), Er (erbium), Tm (thulium), Yb (ytterbium), and Lu (lutetium). .. When a rare earth element is added in the sintering of silicon nitride, the sinterability is improved and the aspect ratio of the silicon nitride crystal particles is improved. As a result, a sintered body having excellent strength characteristics and wear resistance is obtained. Can be done.
また、前記窒化珪素を構成するＴｉ、Ｚｒ、Ｈｆから選ばれる１種以上の４Ａ族元素を５０ｗｔ％以上含む粒子は、窒化物、炭化物、酸化物のいずれかであるとしている。炭化物と窒化物は化学的に安定であり、耐熱性にも優れることから、耐摩耗性部材として摺動させた際に発生する熱による影響を受けにくい。また、４Ａ族元素の窒化物を分散含有させるときに、４Ａ族元素の酸化物を含有させ、焼結時に窒化物へと析出させるとより焼結性を向上させることができる。また、４Ａ族元素は、他の焼結助剤元素および酸素と反応して４Ａ族元素−焼結助剤元素−酸素の結晶質化合物を形成しやすい。 Further, the particles containing 50 wt% or more of one or more Group 4A elements selected from Ti, Zr, and Hf constituting the silicon nitride are said to be any of nitrides, carbides, and oxides. Carbides and nitrides are chemically stable and have excellent heat resistance, so they are not easily affected by the heat generated when they are slid as wear-resistant members. Further, when the nitride of the Group 4A element is dispersed and contained, the sinterability can be further improved by containing the oxide of the Group 4A element and precipitating it on the nitride at the time of sintering. Further, the Group 4A element easily reacts with other sintering aid elements and oxygen to form a crystalline compound of Group 4A element-sintering aid element-oxygen.
また、前記窒化珪素は、窒化珪素結晶粒子と粒界相を具備する窒化珪素焼結体の任意の断面を撮影したとき、Ｔｉ、Ｚｒ、Ｈｆから選ばれる１種の４Ａ族元素が５０ｗｔ％以上含まれる粒子を等しい楕円形状で近似したときの短軸径と長軸径の比が０．３〜１．０であるものが９０％以上含まれていることが好ましい。なお、楕円形状に近似する方法としては、粒界の任意の点から最小二乗法を利用して近似するなどにより求める。このような組織構造により、強度特性を向上させ耐脱粒性に優れた窒化珪素焼結体を提供することが可能である。楕円形状で近似した短軸径と長軸径の比が０．３〜１．０であるものの割合が９０％未満では粒界の強度、特に破壊靭性値が低下し脱粒の原因となる。 Further, the silicon nitride contains 50 wt% or more of one type of Group 4A element selected from Ti, Zr, and Hf when an arbitrary cross section of the silicon nitride sintered body having the silicon nitride crystal grains and the grain boundary phase is photographed. It is preferable that 90% or more of the contained particles have a ratio of the minor axis diameter to the major axis diameter of 0.3 to 1.0 when they are approximated by the same elliptical shape. As a method of approximating the elliptical shape, it is obtained by approximating from an arbitrary point of the grain boundary using the least squares method. With such a structure, it is possible to provide a silicon nitride sintered body having improved strength characteristics and excellent shedding resistance. If the ratio of the minor axis diameter to the major axis diameter approximated by the elliptical shape is 0.3 to 1.0, but the ratio is less than 90%, the strength of the grain boundaries, particularly the fracture toughness value, decreases, which causes grain removal.
次に製造方法について説明する。実施形態にかかる窒化珪素焼結体は上記構成を有すれば特に製造方法は限定されるものではないが、効率的に得るための方法として次のものが挙げられる。
まず、窒化珪素粉末を用意する。窒化珪素粉末は酸素含有量が４ｗｔ％以下で、α相型窒化珪素を８５ｗｔ％以上含み、平均粒子径が０．８μｍ以下であることが好ましい。α相型窒化珪素粉末を焼結工程でβ相型窒化珪素結晶粒子に粒成長させることにより、耐摩耗性の優れた窒化珪素焼結体を得ることができる。本発明の窒化珪素焼結体では、粒界相の粒子中心間最近接距離を制御している。このような制御を行うには、焼結助剤の分散の制御が有効である。焼結助剤の分散の制御には、添加量の制御および窒化珪素粉末との均一分散を行うことが有効である。
焼結助剤の添加量は、４Ａ族元素を１．０〜４．０ｗｔ％、２Ａ族元素、５Ａ族元素、６Ａ族元素、３Ｂ族元素、希土類元素のいずれか１種類以上を１．０〜５．０ｗｔ％であることが好ましい。また、焼結助剤粉末の平均粒子径は１．８μｍ以下であることが好ましい。
Next, the manufacturing method will be described. The silicon nitride sintered body according to the embodiment is not particularly limited in terms of production method as long as it has the above configuration, but the following methods can be mentioned as methods for efficiently obtaining the sintered body.
First, silicon nitride powder is prepared. The silicon nitride powder preferably has an oxygen content of 4 wt% or less, contains 85 wt% or more of α-phase silicon nitride, and has an average particle diameter of 0.8 μm or less. By growing the α-phase silicon nitride powder into β-phase silicon nitride crystal particles in the sintering step, a silicon nitride sintered body having excellent wear resistance can be obtained. In the silicon nitride sintered body of the present invention, the closest contact distance between the particle centers of the grain boundary phase is controlled. In order to perform such control, it is effective to control the dispersion of the sintering aid. In order to control the dispersion of the sintering aid, it is effective to control the addition amount and uniformly disperse with the silicon nitride powder.
The amount of the sintering aid added is 1.0 to 4.0 wt% for Group 4A elements, 1.0 for any one or more of Group 2A elements, Group 5A elements, Group 6A elements, Group 3B elements, and rare earth elements. It is preferably ~ 5.0 wt%. The average particle size of the sintering aid powder is preferably 1.8 μm or less.
窒化珪素粉末と焼結助剤粉末の均一分散には、混合工程を長時間行うことが有効である。また、焼結助剤を予備混合することも有効である。ビーズミル、ボールミル、ポットミルなどによる解砕混合工程が有効であるが、効率的に製造を行うためにはビーズミルとボールミルが好ましい。また、解砕混合時間は５０時間以上の長時間行うことが有効であるが、さらに８０時間以上が好ましい。予備混合の方法は、予め焼結助剤と分割した溶媒と分割した窒化珪素粉末を加えて混合したのち、残りの溶媒と窒化珪素粉末を混合する方法が好ましい。混合工程は、大部分を占める窒化珪素粉末が混合しやすい条件に合わせて設定しているため、形状・流動性等が違う焼結助剤を同時に混合すると均一に分散が行われない可能性がある。たとえば、焼結助剤の合計が５ｗｔ％とした場合、焼結助剤と５ｗｔ％の窒化珪素粉末と投入予定の７．５ｗｔ％の溶媒とを混合しておく方法である。溶媒量の比率が全量を一度に投入した場合よりも少なく、効率的に混合が進むためである。予備混合は後に続けて行う混合とは別の設備・方法で行うことも可能であるが、製造するうえで効率が悪くなるため好ましくない。 It is effective to carry out the mixing step for a long time for uniform dispersion of the silicon nitride powder and the sintering aid powder. It is also effective to premix the sintering aid. A crushing and mixing step using a bead mill, a ball mill, a pot mill or the like is effective, but a bead mill and a ball mill are preferable for efficient production. Further, it is effective to carry out the crushing and mixing time for a long time of 50 hours or more, but more preferably 80 hours or more. As a premixing method, a method in which a sintering aid, a divided solvent and the divided silicon nitride powder are added and mixed in advance, and then the remaining solvent and the silicon nitride powder are mixed is preferable. Since the mixing process is set according to the conditions under which the silicon nitride powder, which accounts for the majority, is easily mixed, there is a possibility that uniform dispersion will not be performed if sintering aids with different shapes and fluidities are mixed at the same time. is there. For example, when the total amount of the sintering aids is 5 wt%, it is a method of mixing the sintering aid, the 5 wt% silicon nitride powder, and the 7.5 wt% solvent to be added. This is because the ratio of the amount of the solvent is smaller than that when the whole amount is added at one time, and the mixing proceeds efficiently. Premixing can be performed by a facility / method different from that of subsequent mixing, but it is not preferable because the efficiency of production is deteriorated.
また、均一分散を行うためには混合時にスラリー粘度を調整する方法も有効である。粉末の解砕・混合が進むとスラリー粘度が上がる。スラリー粘度が上がらない状態で解砕・混合を続けていても原料の一次凝集が十分に解消されず均一な分散は望めない。また、スラリー粘度が上がった状態で解砕・混合を続けていても、解砕・混合の効率が悪くなり十分な均一分散が望めない。このため、解砕・混合中にスラリー粘度を定期的に測定し、粘度の変化により溶媒および分散材を適宜追加する方法が有効である。このような調整は、設備、環境、原材料の状態によって変化するため製造ロットごとに行うことが有効である。 Further, in order to carry out uniform dispersion, a method of adjusting the slurry viscosity at the time of mixing is also effective. As the powder is crushed and mixed, the viscosity of the slurry increases. Even if crushing and mixing are continued without increasing the slurry viscosity, the primary agglutination of the raw materials is not sufficiently eliminated and uniform dispersion cannot be expected. Further, even if crushing / mixing is continued with the slurry viscosity increased, the efficiency of crushing / mixing deteriorates and sufficient uniform dispersion cannot be expected. Therefore, it is effective to measure the slurry viscosity periodically during crushing and mixing, and add a solvent and a dispersant as appropriate according to the change in viscosity. Since such adjustments vary depending on the equipment, environment, and raw material conditions, it is effective to make such adjustments for each production lot.
解砕・混合工程により、窒化珪素粉末同士、焼結助剤粉末同士、窒化珪素粉末および焼結助剤粉末が結合した二次粒子となることを防ぐことができる。窒化珪素粉末と焼結助剤粉末のほとんどが一次粒子となることにより均一分散を行うことができる。
次に、窒化珪素粉末と焼結助剤粉末を混合した原料混合物にバインダを添加する。原料混合物とバインダとの混合はボールミルなどを使用する。バインダを混合して製造されたスラリーは粒子凝集を防ぐためにホモジナイザー、せん断ミキサー、プレネタリーミキサーなどを用いて分散処理を行う。分散処理を行ったスラリーはスプレードライヤーなどを用いて造粒し、得られた造粒粉を所望の形状に成形する。成形工程は、金型プレスや冷間静水圧プレス（ＣＩＰ）等により実施する。成形圧力は１００ＭＰａ以上が好ましい。成形工程で得た成形体を脱脂する。脱脂工程は３００〜６００℃の範囲の温度で実施することが好ましい。脱脂工程は大気中や非酸化性雰囲気中で実施され、雰囲気は特に限定されるものではない。
By the crushing / mixing step, it is possible to prevent the silicon nitride powders, the sintering aid powders from each other, the silicon nitride powder and the sintering aid powder from becoming bonded secondary particles. Since most of the silicon nitride powder and the sintering aid powder are primary particles, uniform dispersion can be performed.
Next, a binder is added to the raw material mixture in which the silicon nitride powder and the sintering aid powder are mixed. A ball mill or the like is used to mix the raw material mixture and the binder. The slurry produced by mixing the binder is subjected to a dispersion treatment using a homogenizer, a shear mixer, a planetary mixer or the like in order to prevent particle aggregation. The dispersion-treated slurry is granulated using a spray dryer or the like, and the obtained granulated powder is molded into a desired shape. The molding process is carried out by a die press, a cold hydrostatic press (CIP), or the like. The molding pressure is preferably 100 MPa or more. The molded product obtained in the molding process is degreased. The degreasing step is preferably carried out at a temperature in the range of 300 to 600 ° C. The degreasing step is carried out in the air or a non-oxidizing atmosphere, and the atmosphere is not particularly limited.
次に、脱脂工程で得た脱脂体を１６００〜１９００℃の範囲の温度で焼結する。焼結温度が１６００℃未満であると、窒化珪素結晶粒子の粒成長が不十分になる恐れがある。すなわち、α相型窒化珪素からβ相型窒化珪素への反応が不十分であり、緻密な焼結体組織が得られない可能性がある。この場合、窒化珪素焼結体の材料としての信頼性が低下する。焼結温度が１９００℃を超えると窒化珪素結晶粒子が粒成長しすぎて、加工性が低下する恐れがある。焼結工程は、常圧焼結および加圧焼結のいずれで実施してもよい。焼結工程は非酸化性雰囲気中で実施することが好ましい。非酸化性雰囲気としては、窒素雰囲気やアルゴン雰囲気が挙げられる。 Next, the degreased body obtained in the degreasing step is sintered at a temperature in the range of 1600 to 1900 ° C. If the sintering temperature is less than 1600 ° C., the grain growth of silicon nitride crystal particles may be insufficient. That is, the reaction from α-phase silicon nitride to β-phase silicon nitride may be insufficient, and a dense sintered body structure may not be obtained. In this case, the reliability of the silicon nitride sintered body as a material is lowered. If the sintering temperature exceeds 1900 ° C., silicon nitride crystal particles may grow too much and the workability may be deteriorated. The sintering step may be carried out by either normal pressure sintering or pressure sintering. The sintering step is preferably carried out in a non-oxidizing atmosphere. Examples of the non-oxidizing atmosphere include a nitrogen atmosphere and an argon atmosphere.
焼結工程の後に、非酸化性雰囲気中にて１０ＭＰａ以上の熱間静水圧プレス（ＨＩＰ）処理を施すことが好ましい。非酸化性雰囲気としては、窒素雰囲気やアルゴン雰囲気が挙げられる。ＨＩＰ処理温度は１５００〜１９００℃の範囲であることが好ましい。ＨＩＰ処理を実施することによって、窒化珪素焼結体内の気孔を消滅させることができる。ＨＩＰ処理圧力が１０ＭＰａ未満であると、そのような効果を十分に得ることができない。 After the sintering step, it is preferable to perform a hot hydrostatic pressure press (HIP) treatment of 10 MPa or more in a non-oxidizing atmosphere. Examples of the non-oxidizing atmosphere include a nitrogen atmosphere and an argon atmosphere. The HIP processing temperature is preferably in the range of 1500 to 1900 ° C. By carrying out the HIP treatment, the pores in the silicon nitride sintered body can be eliminated. If the HIP processing pressure is less than 10 MPa, such an effect cannot be sufficiently obtained.
このようにして製造された窒化珪素焼結体に対して、必要な箇所に研磨加工を施して耐摩耗性部材を作製する。研磨加工は、ダイヤモンド砥粒を用いて実施することが好ましい。 The silicon nitride sintered body produced in this manner is polished at necessary points to produce a wear-resistant member. The polishing process is preferably carried out using diamond abrasive grains.
（実施例）
（実施例１〜９、比較例１〜９）
表１、表２に示した焼結助剤および解砕混合方法を用意して原料粉末を調製した。なお、焼結助剤の添加量は窒化珪素粉末と焼結助剤の合計量を１００ｗｔ％としたときの比率である。
(Example)
(Examples 1 to 9, Comparative Examples 1 to 9)
Raw material powders were prepared by preparing the sintering aids and crushing and mixing methods shown in Tables 1 and 2. The amount of the sintering aid added is the ratio when the total amount of the silicon nitride powder and the sintering aid is 100 wt%.
得られた原料混合物にボールミルにて樹脂バインダを混合してスラリー作製した。得られたスラリーをスプレードライヤーにて乾燥噴霧して造粒粉末を作製した。造粒粉末を成型圧力１５０ＭＰａにて成型工程を行った。得られた成形体に５００℃で脱脂工程を行った。得られた脱脂体に対し、１８００℃×４時間の常圧焼結、１６００℃×２０ＭＰａ×２時間のＨＩＰ処理を行った。この工程により実施例および比較例に係る窒化珪素焼結体を作製した。なお、実施例ではスプレードライヤーにて造粒する前のスラリーをホモジナイザーにて分散処理を行った。
各窒化珪素焼結体に対して、任意の断面を切断加工し、９２．８μｍ２（＝１１．２５μｍ×８．２５μｍ）のＴｉ、Ｚｒ、Ｈｆの拡大写真（ＴＥＭ写真）を撮影した。拡大写真から単位面積５０.４１μｍ２（＝７．１μｍ×７．１μｍ）を使って、単位面積当たりのＴｉ、Ｚｒ、Ｈｆが５０ｗｔ％以上含まれる粒子個数、粒子同士の粒子間最近接距離が１μｍ以上である組み合わせの比率、粒子の最大長が０．３μｍ以上２μｍ以下であるものの比率、含まれる粒子を等しい楕円形状で近似したときの短軸径と長軸径の比が０．３〜１．０であるものの比率を求めた。その結果を表３に示す。
A resin binder was mixed with the obtained raw material mixture by a ball mill to prepare a slurry. The obtained slurry was dried and sprayed with a spray dryer to prepare a granulated powder. The granulated powder was molded at a molding pressure of 150 MPa. The obtained molded product was subjected to a degreasing step at 500 ° C. The obtained degreased body was subjected to atmospheric pressure sintering at 1800 ° C. × 4 hours and HIP treatment at 1600 ° C. × 20 MPa × 2 hours. By this step, silicon nitride sintered bodies according to Examples and Comparative Examples were produced. In the examples, the slurry before granulation with a spray dryer was dispersed with a homogenizer.
An arbitrary cross section was cut from each silicon nitride sintered body, and an enlarged photograph (TEM photograph) of 92.8 μm 2 (= 11.25 μm × 8.25 μm) of Ti, Zr, and Hf was taken. From the enlarged photograph, using a unit area of 50.41 μm2 (= 7.1 μm × 7.1 μm), the number of particles containing 50 wt% or more of Ti, Zr, and Hf per unit area, and the closest contact distance between particles is 1 μm. The ratio of the above combinations, the ratio of particles with a maximum length of 0.3 μm or more and 2 μm or less, and the ratio of the minor axis diameter to the major axis diameter when the contained particles are approximated by the same elliptical shape are 0.3 to 1. The ratio of those with 0.0 was calculated. The results are shown in Table 3.
実施例１〜９に係る窒化珪素焼結体は、４Ａ族元素粒界相の粒子同士の粒子間最近接距離が１μｍ以上である組み合わせが５０％、粒子の最大長が０．３μｍ以上２μｍ以下であるものが９０％以上、楕円形状で近似したときの短軸径と長軸径の比が０．３〜１．０であるものが９０％以上であった。また、ＴＥＭ観察した結果、実施例にかかる窒化珪素焼結体の４Ａ族元素は酸化物、窒化物、水素化物、炭化物であった。
比較例１〜９に関しては４Ａ族元素粒界相の粒子同士の粒子間最近接距離が１μｍ以上である組み合わせが必ずしも５０％以上ではあらず、また粒子の最大長が０．３μｍ以上２μｍ以下であるものが必ずしも９０％以上とはならず、さらに楕円形状で近似したときの短軸径と長軸径の比が０．３〜１．０であるものが必ずしも９０％以上にならなかった。
In the silicon nitride sintered body according to Examples 1 to 9, 50% of the combinations have a closest contact distance between particles of Group 4A element grain boundary phase between particles of 1 μm or more, and the maximum particle length is 0.3 μm or more and 2 μm or less. 90% or more of the particles, and 90% or more of the particles had a ratio of the minor axis diameter to the major axis diameter of 0.3 to 1.0 when approximated by an elliptical shape. Further, as a result of TEM observation, the Group 4A elements of the silicon nitride sintered body according to the examples were oxides, nitrides, hydrides, and carbides.
Regarding Comparative Examples 1 to 9, the combination in which the closest distance between the particles of the group 4A element grain boundary phase is 1 μm or more is not necessarily 50% or more, and the maximum length of the particles is 0.3 μm or more and 2 μm or less. Some particles did not necessarily exceed 90%, and those having a ratio of the minor axis diameter to the major axis diameter of 0.3 to 1.0 when approximated by an elliptical shape did not necessarily exceed 90%.
次に各窒化珪素焼結体の相対密度、三点曲げ強度（σｆ）、耐脱粒性（加工による表面粗さ、転がり寿命時間、表面剥離状態）を測定した。なお、三点曲げ強度測定用の試料（窒化珪素焼結体）は３ｍｍ×４ｍｍ×５０ｍｍのサイズに加工しＪＩＳ−Ｒ−１６０１に準じた方法により測定した。加工による表面粗さによる耐脱粒性測定用には摺動部品であるベアリングボールを作製した。ベアリングボールの直径は９．５２５ｍｍ、表面粗さ（Ｒａ）は０．０１μｍ以下になるように研磨した。
研磨加工に関しては、試料として表面粗さ（Ｒａ）は０．０１μｍ以下に研磨加工する前のものを用意して、ダイヤモンド砥石（＃１２０）を使って研磨加工を行った場合の表面粗さを比較した。研磨加工条件は、試料の加工面積を一定にして荷重を４０Ｎとし、研削盤の回転速度を３００ｒｐｍとして加工し、表面粗さ（Ｒａ）の変化がなくなる時間まで加工を行った後の、表面粗さ（Ｒａ）を測定した。この研磨加工により脱粒状態を測定できる。脱粒状態は表面粗さに相関性があり、数値が大きいほど脱粒が生じやすいことを意味する。
Next, the relative density, three-point bending strength (σf), and shedding resistance (surface roughness due to processing, rolling life time, surface peeling state) of each silicon nitride sintered body were measured. The sample for measuring the three-point bending strength (silicon nitride sintered body) was processed into a size of 3 mm × 4 mm × 50 mm and measured by a method according to JIS-R-1601. A bearing ball, which is a sliding component, was manufactured for measuring the shedding resistance due to the surface roughness due to processing. The bearing balls were polished so that the diameter was 9.525 mm and the surface roughness (Ra) was 0.01 μm or less.
Regarding the polishing process, prepare a sample with a surface roughness (Ra) of 0.01 μm or less before polishing, and use a diamond grindstone (# 120) to polish the surface roughness. Compared. The polishing processing conditions are that the processing area of the sample is constant, the load is 40 N, the rotation speed of the grinder is 300 rpm, and the surface roughness (Ra) is processed until the surface roughness (Ra) does not change. (Ra) was measured. The shedding state can be measured by this polishing process. The shedding state has a correlation with the surface roughness, and the larger the value, the more likely it is that shedding occurs.
また、転がり寿命による耐脱粒性の測定を行うにあたり、ベアリングボールの表面を表面粗さ（Ｒａ）が０．０１μｍ以下になるように研磨加工した仕上げ加工面を有するものを使用した。
各実施例および比較例に係るベアリングボールを３個用意し、軸受鋼（ＳＵＪ２）の上面に設定した直径４０ｍｍの軌道上に上記３個のベアリングボールを等間隔で配置する。これをタービン油の油浴潤滑条件下でベアリングボールに５．９ＧＰａの最大接触応力が作用するように荷重を印加した状態で回転数１２００ｒｐｍにてベアリングボールの表面に脱粒が観察されるまでの時間として耐脱粒性を測定した。なお、転がり寿命による耐脱粒性評価は連続１０００時間を上限として行った。
Further, in measuring the shedding resistance due to the rolling life, a bearing ball having a finished surface obtained by polishing the surface so that the surface roughness (Ra) was 0.01 μm or less was used.
Three bearing balls according to each Example and Comparative Example are prepared, and the above three bearing balls are arranged at equal intervals on a track having a diameter of 40 mm set on the upper surface of the bearing steel (SUJ2). This is the time until degranulation is observed on the surface of the bearing ball at a rotation speed of 1200 rpm with a load applied so that a maximum contact stress of 5.9 GPa acts on the bearing ball under the oil bath lubrication condition of turbine oil. The bleeding resistance was measured as. The bleeding resistance evaluation based on the rolling life was performed up to 1000 hours continuously.
また、表面剥離状態による耐脱粒性の測定を行うにあたり、窒化珪素焼結体からなる板状の耐摩耗性部材を使用した。各実施例および比較例に係る直径６０ｍｍ×厚さ５ｍｍの円板状の上面に設定した直径４０ｍｍの軌道上に直径が９．５２５ｍｍである３個の転動鋼球（ＳＵＪ２）を配置してスラスト型軸受試験機を構成した。上記転動鋼球に５．９ＧＰａの荷重を印加した状態で回転数１２００ｒｐｍの条件下で回転させ、４００時間後に軌道面を観察して粒界相の脱粒があるかを確認した。
相対密度、三点曲げ強度（σｆ）、耐脱粒性（加工による表面粗さ、転がり寿命時間、表面剥離状態）の結果を表４に示す。
Further, in measuring the shedding resistance depending on the surface peeling state, a plate-shaped wear-resistant member made of a silicon nitride sintered body was used. Three rolling steel balls (SUJ2) having a diameter of 9.525 mm are arranged on an orbit having a diameter of 40 mm set on a disk-shaped upper surface having a diameter of 60 mm and a thickness of 5 mm according to each Example and Comparative Example. A thrust type bearing tester was constructed. The rolling steel ball was rotated under the condition of a rotation speed of 1200 rpm with a load of 5.9 GPa applied, and after 400 hours, the orbital surface was observed to confirm whether or not there was grain boundary phase shedding.
Table 4 shows the results of the relative density, the three-point bending strength (σf), and the shedding resistance (surface roughness due to processing, rolling life time, surface peeling state).
実施例および比較例に係る窒化珪素焼結体は、いずれも相対密度が９９．５％以上であり、十分な緻密化が進んでいる。また、三点曲げ強度も９００ＭＰａ以上と高い値となっている。
実施例１〜９に係る窒化珪素焼結体は、加工による表面粗さ（Ｒａ）で、いずれも０．１８μｍ以下となった。また、転がり寿命による耐脱粒性評価でも１０００時間後でも脱粒は観察されなかった。また、表面剥離状態での耐脱粒性評価でも脱粒は観察されなかった。図４に剥離のない軌道面観察の一例を示す。
対して比較例１〜９では、加工による表面粗さ（Ｒａ）は０．２２μｍと実施例に比較して大きかった。また、転がり寿命による耐脱粒性評価でも１０００時間を超えるものは現れなかった。また、表面剥離状態での耐脱粒性評価では、粒界部分に脱粒があるものが見受けられた。図５に剥離のない軌道面観察の一例を示す。
これらの実験結果により、実施例は耐脱粒性において非常に優れており、厳しい環境条件での信頼性が十分に高いと言える。
The silicon nitride sintered bodies according to the examples and the comparative examples both have a relative density of 99.5% or more, and are sufficiently densified. In addition, the three-point bending strength is as high as 900 MPa or more.
The silicon nitride sintered bodies according to Examples 1 to 9 had a surface roughness (Ra) of 0.18 μm or less due to processing. In addition, no shedding was observed even after 1000 hours in the evaluation of shedding resistance based on the rolling life. In addition, no shedding was observed in the evaluation of shedding resistance in the state of surface peeling. FIG. 4 shows an example of track surface observation without peeling.
On the other hand, in Comparative Examples 1 to 9, the surface roughness (Ra) due to processing was 0.22 μm, which was larger than that of Examples. Moreover, in the evaluation of the shedding resistance based on the rolling life, no one exceeding 1000 hours appeared. In addition, in the evaluation of the shedding resistance in the state of surface peeling, it was found that there was shedding at the grain boundary. FIG. 5 shows an example of track surface observation without peeling.
From these experimental results, it can be said that the examples are very excellent in shedding resistance and are sufficiently reliable in harsh environmental conditions.
以上、本発明のいくつかの実施形態を例示したが、これらの実施形態は、例として提示したものであり、発明の範囲を限定することは意図していない。これら新規な実施形態は、その他の様々な形態で実施されることが可能であり、発明の要旨を逸脱しない範囲で、種々の省略、置き換え、変更などを行うことができる。これら実施形態やその変形例は、発明の範囲や要旨に含まれるとともに、特許請求の範囲に記載された発明とその均等の範囲に含まれる。また、前述の各実施形態は、相互に組み合わせて実施することができる。 Although some embodiments of the present invention have been illustrated above, these embodiments are presented as examples and are not intended to limit the scope of the invention. These novel embodiments can be implemented in various other embodiments, and various omissions, replacements, changes, etc. can be made without departing from the gist of the invention. These embodiments and modifications thereof are included in the scope and gist of the invention, and are also included in the scope of the invention described in the claims and the equivalent scope thereof. In addition, the above-described embodiments can be implemented in combination with each other.
１…ベアリングボール〈窒化珪素焼結体、摺動部材〉
２…摺動面
1 ... Bearing ball <Silicon nitride sintered body, sliding member>
2 ... Sliding surface
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| JP2002060276A (en) * | 2000-08-21 | 2002-02-26 | Toshiba Corp | Sintered silicon nitride compact as well as sliding member and bearing ball using the same |
| JP2004002067A (en) * | 2002-05-29 | 2004-01-08 | Toshiba Corp | Wear-resistant member and its production process |
| JP2016064971A (en) * | 2014-09-25 | 2016-04-28 | 株式会社東芝 | Silicon nitride sintered body and abrasion resistant member using the same |
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| JP2002060276A (en) * | 2000-08-21 | 2002-02-26 | Toshiba Corp | Sintered silicon nitride compact as well as sliding member and bearing ball using the same |
| JP2004002067A (en) * | 2002-05-29 | 2004-01-08 | Toshiba Corp | Wear-resistant member and its production process |
| JP2016064971A (en) * | 2014-09-25 | 2016-04-28 | 株式会社東芝 | Silicon nitride sintered body and abrasion resistant member using the same |
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