JPH0247426B2 - - Google Patents
Info
- Publication number
- JPH0247426B2 JPH0247426B2 JP56192364A JP19236481A JPH0247426B2 JP H0247426 B2 JPH0247426 B2 JP H0247426B2 JP 56192364 A JP56192364 A JP 56192364A JP 19236481 A JP19236481 A JP 19236481A JP H0247426 B2 JPH0247426 B2 JP H0247426B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- oxide
- powder
- sintered body
- sintering
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000843 powder Substances 0.000 claims description 41
- 238000005245 sintering Methods 0.000 claims description 23
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 20
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 20
- 239000000919 ceramic Substances 0.000 claims description 15
- 239000012298 atmosphere Substances 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 230000001590 oxidative effect Effects 0.000 claims description 10
- 229910021332 silicide Inorganic materials 0.000 claims description 9
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 5
- 239000011651 chromium Substances 0.000 claims description 5
- 239000011812 mixed powder Substances 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 4
- 229910052580 B4C Inorganic materials 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052790 beryllium Inorganic materials 0.000 claims description 3
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims description 3
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 150000001247 metal acetylides Chemical class 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 239000010955 niobium Substances 0.000 claims description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 description 20
- 238000010438 heat treatment Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 4
- 229910052814 silicon oxide Inorganic materials 0.000 description 4
- INZDTEICWPZYJM-UHFFFAOYSA-N 1-(chloromethyl)-4-[4-(chloromethyl)phenyl]benzene Chemical compound C1=CC(CCl)=CC=C1C1=CC=C(CCl)C=C1 INZDTEICWPZYJM-UHFFFAOYSA-N 0.000 description 3
- 229910026551 ZrC Inorganic materials 0.000 description 3
- OTCHGXYCWNXDOA-UHFFFAOYSA-N [C].[Zr] Chemical compound [C].[Zr] OTCHGXYCWNXDOA-UHFFFAOYSA-N 0.000 description 3
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 3
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- WHJFNYXPKGDKBB-UHFFFAOYSA-N hafnium;methane Chemical compound C.[Hf] WHJFNYXPKGDKBB-UHFFFAOYSA-N 0.000 description 3
- 238000007731 hot pressing Methods 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- UNASZPQZIFZUSI-UHFFFAOYSA-N methylidyneniobium Chemical compound [Nb]#C UNASZPQZIFZUSI-UHFFFAOYSA-N 0.000 description 3
- NFFIWVVINABMKP-UHFFFAOYSA-N methylidynetantalum Chemical compound [Ta]#C NFFIWVVINABMKP-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 3
- 229910000480 nickel oxide Inorganic materials 0.000 description 3
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 3
- 230000035939 shock Effects 0.000 description 3
- 229910003468 tantalcarbide Inorganic materials 0.000 description 3
- 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 3
- LTPBRCUWZOMYOC-UHFFFAOYSA-N Beryllium oxide Chemical compound O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- TWRSDLOICOIGRH-UHFFFAOYSA-N [Si].[Si].[Hf] Chemical compound [Si].[Si].[Hf] TWRSDLOICOIGRH-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(iv) oxide Chemical compound O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 2
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- WEAMLHXSIBDPGN-UHFFFAOYSA-N (4-hydroxy-3-methylphenyl) thiocyanate Chemical compound CC1=CC(SC#N)=CC=C1O WEAMLHXSIBDPGN-UHFFFAOYSA-N 0.000 description 1
- OFEAOSSMQHGXMM-UHFFFAOYSA-N 12007-10-2 Chemical compound [W].[W]=[B] OFEAOSSMQHGXMM-UHFFFAOYSA-N 0.000 description 1
- FRWYFWZENXDZMU-UHFFFAOYSA-N 2-iodoquinoline Chemical compound C1=CC=CC2=NC(I)=CC=C21 FRWYFWZENXDZMU-UHFFFAOYSA-N 0.000 description 1
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910021359 Chromium(II) silicide Inorganic materials 0.000 description 1
- 229910019001 CoSi Inorganic materials 0.000 description 1
- 229910018999 CoSi2 Inorganic materials 0.000 description 1
- 229910019918 CrB2 Inorganic materials 0.000 description 1
- 229910019018 Mg 2 Si Inorganic materials 0.000 description 1
- 229910003178 Mo2C Inorganic materials 0.000 description 1
- 229910016006 MoSi Inorganic materials 0.000 description 1
- 229910005108 Ni3Si2 Inorganic materials 0.000 description 1
- 229910008484 TiSi Inorganic materials 0.000 description 1
- 229910008479 TiSi2 Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910006249 ZrSi Inorganic materials 0.000 description 1
- LRTTZMZPZHBOPO-UHFFFAOYSA-N [B].[B].[Hf] Chemical compound [B].[B].[Hf] LRTTZMZPZHBOPO-UHFFFAOYSA-N 0.000 description 1
- CVTZKFWZDBJAHE-UHFFFAOYSA-N [N].N Chemical compound [N].N CVTZKFWZDBJAHE-UHFFFAOYSA-N 0.000 description 1
- UPEMFLOMQVFMCZ-UHFFFAOYSA-N [O--].[O--].[O--].[Pm+3].[Pm+3] Chemical compound [O--].[O--].[O--].[Pm+3].[Pm+3] UPEMFLOMQVFMCZ-UHFFFAOYSA-N 0.000 description 1
- CHXGWONBPAADHP-UHFFFAOYSA-N [Si].[Si].[Cr] Chemical compound [Si].[Si].[Cr] CHXGWONBPAADHP-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 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
- FHTCLMVMBMJAEE-UHFFFAOYSA-N bis($l^{2}-silanylidene)manganese Chemical compound [Si]=[Mn]=[Si] FHTCLMVMBMJAEE-UHFFFAOYSA-N 0.000 description 1
- YXTPWUNVHCYOSP-UHFFFAOYSA-N bis($l^{2}-silanylidene)molybdenum Chemical compound [Si]=[Mo]=[Si] YXTPWUNVHCYOSP-UHFFFAOYSA-N 0.000 description 1
- MANYRMJQFFSZKJ-UHFFFAOYSA-N bis($l^{2}-silanylidene)tantalum Chemical compound [Si]=[Ta]=[Si] MANYRMJQFFSZKJ-UHFFFAOYSA-N 0.000 description 1
- DFJQEGUNXWZVAH-UHFFFAOYSA-N bis($l^{2}-silanylidene)titanium Chemical compound [Si]=[Ti]=[Si] DFJQEGUNXWZVAH-UHFFFAOYSA-N 0.000 description 1
- LUWOVYQXZRKECH-UHFFFAOYSA-N bis($l^{2}-silanylidene)vanadium Chemical compound [Si]=[V]=[Si] LUWOVYQXZRKECH-UHFFFAOYSA-N 0.000 description 1
- LGLOITKZTDVGOE-UHFFFAOYSA-N boranylidynemolybdenum Chemical compound [Mo]#B LGLOITKZTDVGOE-UHFFFAOYSA-N 0.000 description 1
- VDZMENNHPJNJPP-UHFFFAOYSA-N boranylidyneniobium Chemical compound [Nb]#B VDZMENNHPJNJPP-UHFFFAOYSA-N 0.000 description 1
- XTDAIYZKROTZLD-UHFFFAOYSA-N boranylidynetantalum Chemical compound [Ta]#B XTDAIYZKROTZLD-UHFFFAOYSA-N 0.000 description 1
- QDMRQDKMCNPQQH-UHFFFAOYSA-N boranylidynetitanium Chemical compound [B].[Ti] QDMRQDKMCNPQQH-UHFFFAOYSA-N 0.000 description 1
- LAROCDZIZGIQGR-UHFFFAOYSA-N boron;vanadium Chemical compound B#[V]#B LAROCDZIZGIQGR-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- UFGZSIPAQKLCGR-UHFFFAOYSA-N chromium carbide Chemical compound [Cr]#C[Cr]C#[Cr] UFGZSIPAQKLCGR-UHFFFAOYSA-N 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 229910003440 dysprosium oxide Inorganic materials 0.000 description 1
- NLQFUUYNQFMIJW-UHFFFAOYSA-N dysprosium(iii) oxide Chemical compound O=[Dy]O[Dy]=O NLQFUUYNQFMIJW-UHFFFAOYSA-N 0.000 description 1
- ZXGIFJXRQHZCGJ-UHFFFAOYSA-N erbium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Er+3].[Er+3] ZXGIFJXRQHZCGJ-UHFFFAOYSA-N 0.000 description 1
- 229910001940 europium oxide Inorganic materials 0.000 description 1
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- OWCYYNSBGXMRQN-UHFFFAOYSA-N holmium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ho+3].[Ho+3] OWCYYNSBGXMRQN-UHFFFAOYSA-N 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- YTHCQFKNFVSQBC-UHFFFAOYSA-N magnesium silicide Chemical compound [Mg]=[Si]=[Mg] YTHCQFKNFVSQBC-UHFFFAOYSA-N 0.000 description 1
- PYLLWONICXJARP-UHFFFAOYSA-N manganese silicon Chemical compound [Si].[Mn] PYLLWONICXJARP-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- JAGQSESDQXCFCH-UHFFFAOYSA-N methane;molybdenum Chemical compound C.[Mo].[Mo] JAGQSESDQXCFCH-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910021334 nickel silicide Inorganic materials 0.000 description 1
- RUFLMLWJRZAWLJ-UHFFFAOYSA-N nickel silicide Chemical compound [Ni]=[Si]=[Ni] RUFLMLWJRZAWLJ-UHFFFAOYSA-N 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-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
- 238000013001 point bending Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 1
- SCRZPWWVSXWCMC-UHFFFAOYSA-N terbium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Tb+3].[Tb+3] SCRZPWWVSXWCMC-UHFFFAOYSA-N 0.000 description 1
- ZIKATJAYWZUJPY-UHFFFAOYSA-N thulium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Tm+3].[Tm+3] ZIKATJAYWZUJPY-UHFFFAOYSA-N 0.000 description 1
- 229910021341 titanium silicide Inorganic materials 0.000 description 1
- 229910003470 tongbaite Inorganic materials 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
- WQJQOUPTWCFRMM-UHFFFAOYSA-N tungsten disilicide Chemical compound [Si]#[W]#[Si] WQJQOUPTWCFRMM-UHFFFAOYSA-N 0.000 description 1
- 229910021342 tungsten silicide 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
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- 229910021355 zirconium silicide Inorganic materials 0.000 description 1
- 229910021354 zirconium(IV) silicide Inorganic materials 0.000 description 1
Landscapes
- Ceramic Products (AREA)
Description
発明の技術分野
本発明は、セラミツクス焼結体の製造方法に関
し、更に詳しくは、高密度で、高温時における機
械的強度（以下、高温強度と称す）の低下度合が
少ないセラミツクス焼結体の製造方法に関する。
発明の技術的背景とその問題点
窒化ケイ素を主成分として成るセラミツクス焼
結体は、1900℃程度の高温にまで耐えるという優
れた耐熱性を有すると共に、熱膨脹係数が低いこ
とから優れた耐熱衝撃性をも有している。かかる
性質を利用して、この種の窒化ケイ素を主成分と
して成るセラミツクス焼結体は、ガスタービン
翼、ノズル等の高温時に高強度が要求される構造
部品等に応用が試みられている。このようなセラ
ミツクス焼結体は、現在、例えば、窒化ケイ素−
酸化イツトリウム−酸化アルミニウムから成る混
合物を原料として、所謂ホツトプレス法や普通焼
結法等によつて製造されている。
本発明者らは先に、例えばホツトプレス法にお
いて、結晶粒界の物質を、ガラス質（非晶質）の
ものからSi3N4・Y2O3結晶化合物に変えることに
より、優れた特性を有する窒化ケイ素系焼結体が
得られることを明らかにした。又、本発明者ら
は、特開昭54−47709号公報や特開昭55−27843号
公報において開示したように、焼結体中のガラス
質物の存在量が少ないセラミツクス粉末材料の製
造方法、或いはセラミツクス粉末材料として
Si3N4とY2O3から生成せしめた窒化ケイ素質粉末
を使用することにより、高温強度が向上した焼結
体が得られることをも明らかにした。
しかしながら、上記した焼結法において、普通
焼結法を使用した場合には緻密な焼結体を得るこ
とが困難であり、機械的強度及び耐熱衝撃性が優
れた焼結体が得られないという欠点を有してい
る。又、ホツトプレス焼結法を使用した場合に
は、機械的強度及び耐熱衝撃性が優れた焼結体は
得られるが、焼結体の形状が制約され、且つ量産
には適していないという欠点を有している。
これらの欠点を解消するために、本発明者ら
は、更に、特開昭55−113674号公報において、焼
結体原料としてSi3N4−Y2O3−Al2O3−AlN−
TiO2、ZrO2、MgO系の材料を使用することによ
り、ホツトプレス法により製造した焼結体に匹敵
する、優れた機械的強度及び耐熱性を有する高密
度焼結体を製造することができる普通焼結法を提
案した。しかし、この方法で得られた焼結体は、
1300℃付近における機械的強度が必ずしも満足の
いくものではなかつた。
発明の目的
本発明の目的は、上記した欠点を解消し、高密
度で高温時における機械的強度の低下度合が少な
いセラミツクス焼結体の製造方法を提供するにあ
る。
発明の概要
本発明者らは、鋭意研究を重ねた結果、焼結体
の高温強度を低下せしめる原因が、原料粉末中に
存在する酸素又は酸化ケイ素（SiO2）と焼結用
添加物の反応生成物であるガラス質（非晶質）の
低融点粒界相にあることを見出した。そして、予
め熱処理を施したセラミツクス原料を使用するこ
とにより、上記目的が達成できることを見出し、
本発明を完成するに到つた。
即ち、本発明のセラミツクス焼結体の製造方法
は、非酸化性雰囲気中において熱処理を施した窒
化ケイ素粉末75重量％以上：少なくとも１種以上
の稀土類元素の酸化物粉末0.1〜10重量％：酸化
アルミニウム粉末0.1〜10重量％：窒化アルミニ
ウム粉末0.1〜10重量％：並びにチタン、ジルコ
ニウム、クロム、ハフニウム、タンタル、ニオ
ブ、モリブデン、バナジウム及びタングステンの
それぞれの酸化物、炭化物、珪化物及び硼化物；
マグネシウム、ニツケル、コバルト、マンガン及
びベリリウムのそれぞれの酸化物及び珪化物；及
び炭化硼素から成る群より選ばれた１種もしくは
２種以上の粉末0.05〜５重量％から成る混合粉末
を成形し、該成形体を非酸化性雰囲気中において
焼結することを特徴とするものである。
以下において、本発明を更に詳しく説明する。
本発明における窒化ケイ素（Si3N4）粉末の熱
処理は、非酸化性雰囲気中において、例えば、α
型窒化ケイ素粉末を、1400〜1800℃の温度範囲
で、好ましくは1600〜1700℃で、30分〜２時間程
度行なうものである。非酸化性雰囲気としては、
例えば、窒素、アルゴン、一酸化炭素、窒素−ア
ンモニアガス等が挙げられる。かかる熱処理を施
すことにより、窒化ケイ素粉末に付着もしくは吸
着している酸素或いは酸化ケイ素が脱離して、そ
の濃度が著しく低下した窒化ケイ素粉末が得られ
る。従つて、このような処理を施した窒化ケイ素
粉末を使用した焼結体は、添加物（焼結助剤）と
酸素或いは酸化ケイ素が反応して生ずるガラス質
（非晶質）物の量が除去もしくは極めて低減され
たものであるために、その1300℃付近における機
械的強度が改善されたものとなる。
上記窒化ケイ素粉末は、75重量％以上配合され
るものであり、好ましくは80重量％以上である。
かかる窒化ケイ素粉末の量が、75重量％未満であ
ると、得られるセラミツクス焼結体の高温強度の
改善はみられない。
本発明において使用される稀土類元素の酸化物
としては、例えば、酸化イツトリウム（Y2O3）、
酸化ランタン（La2O3）、酸化セリウム（CeO2）、
酸化プラセオジウム（Pr2O3）、酸化ネオジウム
（Nb2O3）、酸化プロメチウム（Pm2O3）、酸化サ
マリウム（Sm2O3）、酸化ユーロピウム
（En2O3）、酸化ガドリウム（Gd2O3）、酸化テル
ビウム（Tb2O3）、酸化ジスプロシウム
（Dy2O3）、酸化ホルミウム（Ho2O3）、酸化エル
ビウム（Er2O3）、酸化ツリウム（Tm2O3）及び
酸化イツテルビウム（Yb2O3）等が挙げられ、こ
れから成る群より選ばれた１種もしくは２種以上
のものが使用される。これらの中でも、とりわ
け、酸化イツトリウムを使用することが好まし
い。
上記稀土類元素の酸化物及び酸化アルミニウム
（Al2O3）は、いずれも焼結促進剤として機能す
るものである。これらの成分は、その配合比が、
それぞれ10重量％を超えると、得られる焼結体の
高温強度が低下する。これらのものは、総量で３
〜15重量％配合することが好ましい。
窒化アルミニウム（AlN）は、焼結体の主成
分であるSi3N4の焼結過程における蒸発や粒成長
を抑制する機能を有するほか、他の成分と反応し
て焼結体全体の焼結促進に寄与するものである。
AlNの配合比が10重量％を超えると、得られる
焼結体の高温強度が低下する。
本発明において、第５成分として添加される
種々の元素のそれぞれの酸化物、炭化物、珪化物
又は硼化物としては、例えば、酸化チタン
（TiO2）、酸化ジルコニウム（ZrO2）、酸化クロム
（Cr2O3）、酸化ハフニウム（HfO2）、酸化タンタ
ル（Ta2O5）、酸化ニオブ（Nb2O5）、酸化モリブ
デン（MoO3）、酸化バナジウム（V2O5）、酸化
タングステン（WO3）、酸化マグネシウム
（MgO）、酸化ニツケル（NiO）、酸化コバルト
（CoO）、酸化マンガン（MnO2）、酸化ベリリウ
ム（BeO）等の酸化物；炭化チタン（TiC）、炭
化ジルコニウム（ZrC）、炭化クロム（Cr3C2）、
炭化ハフニウム（HfC）、炭化タンタル（TaC）、
炭化ニオブ（NbC）、炭化モリブデン（Mo2C）、
炭化バナジウム（VC）、炭化タングステン
（WC）、炭化硼素（B4C）等の炭化物；珪化チタ
ン（TiSi2）、珪化ジルコニウム（ZrSi2）、珪化ク
ロム（CrSi2）、珪化ハフニウム（HfSi）、珪化タ
ンタル（TaSi2）、珪化ニオブ（NbSi2）、珪化モ
リブデン（MoSi2）、珪化バナジウム（VSi2）、
珪化タングステン（WSi2）、珪化マグネシウム
（Mg2Si）、珪化ニツケル（Ni3Si2）、珪化コバル
ト（CoSi2）、珪化マンガン（MnSi）、珪化ベリ
リウム（BeSi2）等の珪化物；及び硼化チタン
（TiB2）、硼化ジルコニウム（ZrB）、硼化クロム
（CrB2）、硼化ハフニウム（HfB2）、硼化タンタ
ル（TaB2）、硼化ニオブ（NbB2）、硼化モリブ
デン（MoB2）、硼化バナジウム（VB2）、硼化タ
ングステン（WB）等の硼化物等が挙げられ、こ
れらから成る群より選ばれた１種もしくは２種以
上のものが使用される。これらの化合物は、いず
れも焼結体の焼結を促進する機能を有するもので
あり、主成分であるSi3N4の濡れ性を改善して焼
結体の緻密化、焼結時間の短縮及び焼結温度の低
下等をもたらすものである。
これらの物質は、総量で0.05〜５重量％使用す
るものであり、好ましくは0.1〜３重量％である。
これらの物質の添加量が、0.05重量％未満である
と、その添加効果が充分ではなく、一方、５重量
％を超えると、得られる焼結体の高温強度が損な
われる。
上記した配合量から成る粉末の混合は、通常、
混合操作に使用されている方法でよく、例えば、
ボールミル等の粉砕混合機を用いて、必要に応じ
てｎ−ブチルアルコール等の溶剤を添加して行な
うことができる。
このようにして調製された混合粉末に対し、次
いで、好ましくはパラフイン等の粘結剤を添加し
て、適宜な圧力を印加して所定形状の成形体とす
る。尚、粘結剤を添加した場合には、600〜800℃
で加熱処理を施して、粘結剤を揮散除去した後に
焼結することが好ましい。
更に、この成形体を、非酸化性雰囲気中におい
て焼結することにより、焼結体を得る。焼結は、
例えば、1500〜1900℃、好ましくは1600〜1800℃
に加熱して行なうことができる。非酸化性雰囲気
としては、例えば、窒素、アルゴン等が挙げられ
る。酸化性雰囲気では、Si3N4が酸化されてSiO2
になるため不可である。
尚、この焼結時に、50〜500Kg／cm2の圧力を印
加したホツトプレス状態、又は、非酸化性ガス雰
囲気を加圧状態にして焼結を行なつてもよい。或
いは、普通焼結法による焼結を行なつた後に、更
に、加圧雰囲気中において焼結を行なつたもので
あつても、本発明に係る焼結体の特性は何ら損な
われるものではない。
以下において、実施例及び参考例を掲げて、本
発明を更に詳しく説明する。
実施例 １〜12
α相型窒化ケイ素85％を含有する、平均粒度
1.2μの窒化ケイ素粉末を、窒素雰囲気中におい
て、1650℃で１時間加熱処理を施すことにより、
酸素及び酸化ケイ素濃度を低下せしめた窒化ケイ
素粉末を得た。
かかる窒化ケイ素粉末、平均粒度1μのY2O3粉
末、平均粒度0.5μのAl2O3粉末、平均粒度1.5μの
AlN粉末並びに平均粒度1μのTiO2、ZrO2、
Cr2O3、HfO2、Ta2O5、Nb2O5、MoO3、V2O5、
WO3、NiO、CoO、MnO2、BeO、TiC、TiSi2、
TiBのそれぞれの粉末を使用して、表に示すよう
な配合量（重量％）で12種類の混合粉末を調製し
た。かかる混合粉末に対し、それぞれ、ｎ−ブチ
ルアルコールを溶媒として使用し、ゴムライニン
グボールミルを用いて、24時間粉砕混合を行なつ
た。
このようにして調製した原料粉末に、粘結剤と
してパラフインを重量比で７％、それぞれ添加配
合して700Kg／cm2の成形圧を印加して、長さ60mm、
幅40mm、厚さ10mmを有する板状成形体を作成し
た。
かかる成形体を、先ず700℃で加熱処理を施し
て、粘結剤を揮散除去した後、窒素ガス雰囲気下
において、1750℃でそれぞれ焼結を行ない、窒化
ケイ素系セラミツクス焼結体を得た。
参考例 １〜10
熱処理を施していない窒化ケイ素粉末を使用す
るか、或いは、Si3N4粉末、Y2O3粉末、Al2O3粉
末、AlN粉末並びに第５成分として添加される
粉末の配合量を変えて使用した他は、実施例とす
べて同様の操作にて、表に同時に示した組成から
成る焼結体を10種類調製した。
上記操作により得られたそれぞれの焼結体につ
いて相対密度及び抗折強度（機械的強度）を測定
し、その結果も表に併記した。
尚、表中の相対密度は、理論密度を基礎とする
相対値（％）である。又、抗折強度値は、３点曲
げ強度試験によるものであり、試料サイズは３×
３×30（mm）、試験条件はクロスヘツドスピード
0.5mm／min、スパン20mm、温度は常温と1300℃
であり、各温度での測定はすべて４回行ない、そ
の平均値を記載した。
Technical Field of the Invention The present invention relates to a method for manufacturing a ceramic sintered body, and more specifically, to a method for manufacturing a ceramic sintered body that has high density and has a low degree of decrease in mechanical strength at high temperatures (hereinafter referred to as high temperature strength). Regarding the method. Technical background of the invention and its problems Ceramic sintered bodies mainly composed of silicon nitride have excellent heat resistance, being able to withstand high temperatures of around 1900°C, and have excellent thermal shock resistance due to their low coefficient of thermal expansion. It also has Taking advantage of such properties, attempts have been made to apply this type of ceramic sintered body mainly composed of silicon nitride to structural parts such as gas turbine blades and nozzles that require high strength at high temperatures. Currently, such ceramic sintered bodies are made of, for example, silicon nitride.
It is manufactured using a mixture of yttrium oxide and aluminum oxide as a raw material by the so-called hot pressing method, ordinary sintering method, etc. The present inventors have previously achieved excellent properties by changing the material at grain boundaries from a glassy (amorphous) material to a Si 3 N 4 Y 2 O 3 crystal compound, for example in the hot pressing method. It was revealed that a silicon nitride-based sintered body having the following characteristics can be obtained. In addition, the present inventors have proposed a method for producing a ceramic powder material in which the amount of glassy material present in the sintered body is small, as disclosed in JP-A-54-47709 and JP-A-55-27843; Or as a ceramic powder material
It was also revealed that a sintered body with improved high-temperature strength can be obtained by using silicon nitride powder produced from Si 3 N 4 and Y 2 O 3 . However, in the above-mentioned sintering method, it is difficult to obtain a dense sintered body when using the normal sintering method, and it is difficult to obtain a sintered body with excellent mechanical strength and thermal shock resistance. It has drawbacks. In addition, when using the hot press sintering method, a sintered body with excellent mechanical strength and thermal shock resistance can be obtained, but the shape of the sintered body is restricted and it is not suitable for mass production. have. In order to eliminate these drawbacks, the present inventors further developed Si 3 N 4 −Y 2 O 3 −Al 2 O 3 −AlN− as a raw material for the sintered body in Japanese Patent Application Laid-Open No. 113674/1983.
By using TiO 2 , ZrO 2 , and MgO-based materials, it is possible to produce high-density sintered bodies with excellent mechanical strength and heat resistance comparable to sintered bodies produced by hot pressing. A sintering method was proposed. However, the sintered body obtained by this method is
The mechanical strength at around 1300°C was not necessarily satisfactory. OBJECTS OF THE INVENTION It is an object of the present invention to eliminate the above-mentioned drawbacks and to provide a method for manufacturing a ceramic sintered body that has high density and exhibits less decrease in mechanical strength at high temperatures. Summary of the Invention As a result of extensive research, the present inventors have discovered that the cause of the reduction in high-temperature strength of sintered bodies is the reaction between oxygen or silicon oxide (SiO 2 ) present in the raw material powder and sintering additives. It was found that the product is a glassy (amorphous) low melting point grain boundary phase. They discovered that the above objective could be achieved by using ceramic raw materials that had been heat-treated in advance.
The present invention has now been completed. That is, the method for producing a ceramic sintered body of the present invention includes: 75% by weight or more of silicon nitride powder heat-treated in a non-oxidizing atmosphere: 0.1 to 10% by weight of at least one rare earth element oxide powder: 0.1-10% by weight of aluminum oxide powder: 0.1-10% by weight of aluminum nitride powder: and respective oxides, carbides, silicides and borides of titanium, zirconium, chromium, hafnium, tantalum, niobium, molybdenum, vanadium and tungsten;
A mixed powder consisting of 0.05 to 5% by weight of one or more powders selected from the group consisting of oxides and silicides of magnesium, nickel, cobalt, manganese and beryllium; and boron carbide is molded. This method is characterized in that the molded body is sintered in a non-oxidizing atmosphere. In the following, the invention will be explained in more detail. The heat treatment of silicon nitride (Si 3 N 4 ) powder in the present invention is carried out in a non-oxidizing atmosphere, for example, by α
The mold silicon nitride powder is heated at a temperature range of 1400 to 1800°C, preferably 1600 to 1700°C, for about 30 minutes to 2 hours. As a non-oxidizing atmosphere,
Examples include nitrogen, argon, carbon monoxide, nitrogen-ammonia gas, and the like. By performing such heat treatment, oxygen or silicon oxide attached or adsorbed to the silicon nitride powder is desorbed, and a silicon nitride powder whose concentration is significantly reduced is obtained. Therefore, in a sintered body using silicon nitride powder subjected to such treatment, the amount of glassy (amorphous) material produced by the reaction between the additive (sintering aid) and oxygen or silicon oxide is small. Since it is removed or extremely reduced, its mechanical strength at around 1300°C is improved. The silicon nitride powder is blended in an amount of 75% by weight or more, preferably 80% by weight or more.
If the amount of silicon nitride powder is less than 75% by weight, no improvement in the high temperature strength of the resulting ceramic sintered body will be observed. Examples of rare earth element oxides used in the present invention include yttrium oxide (Y 2 O 3 ),
Lanthanum oxide (La 2 O 3 ), cerium oxide (CeO 2 ),
Praseodymium oxide (Pr 2 O 3 ), neodymium oxide (Nb 2 O 3 ), promethium oxide (Pm 2 O 3 ), samarium oxide (Sm 2 O 3 ), europium oxide (En 2 O 3 ), gadolinium oxide (Gd 2 O 3 ), terbium oxide (Tb 2 O 3 ), dysprosium oxide (Dy 2 O 3 ), holmium oxide (Ho 2 O 3 ), erbium oxide (Er 2 O 3 ), thulium oxide (Tm 2 O 3 ) and oxide Examples include itterbium (Yb 2 O 3 ), and one or more selected from the group consisting of these are used. Among these, it is particularly preferable to use yttrium oxide. Both the rare earth element oxide and aluminum oxide (Al 2 O 3 ) function as sintering accelerators. The blending ratio of these ingredients is
When each exceeds 10% by weight, the high temperature strength of the obtained sintered body decreases. These things total 3
It is preferable to mix it in an amount of ~15% by weight. Aluminum nitride (AlN) has the function of suppressing evaporation and grain growth during the sintering process of Si 3 N 4 , which is the main component of the sintered body, and also suppresses the sintering of the entire sintered body by reacting with other components. This contributes to the promotion of
When the blending ratio of AlN exceeds 10% by weight, the high temperature strength of the obtained sintered body decreases. In the present invention, examples of the oxide, carbide, silicide, or boride of various elements added as the fifth component include titanium oxide (TiO 2 ), zirconium oxide (ZrO 2 ), and chromium oxide (Cr 2 O 3 ), hafnium oxide (HfO 2 ), tantalum oxide (Ta 2 O 5 ), niobium oxide (Nb 2 O 5 ), molybdenum oxide (MoO 3 ), vanadium oxide (V 2 O 5 ), tungsten oxide (WO 3 ) Oxides such as magnesium oxide (MgO), nickel oxide (NiO), cobalt oxide (CoO), manganese oxide (MnO 2 ), and beryllium oxide (BeO); titanium carbide (TiC), zirconium carbide (ZrC), Chromium carbide (Cr 3 C 2 ),
Hafnium carbide (HfC), tantalum carbide (TaC),
Niobium carbide (NbC), molybdenum carbide ( Mo2C ),
Carbides such as vanadium carbide (VC), tungsten carbide (WC), and boron carbide (B 4 C); titanium silicide (TiSi 2 ), zirconium silicide (ZrSi 2 ), chromium silicide (CrSi 2 ), hafnium silicide (HfSi), Tantalum silicide (TaSi 2 ), niobium silicide (NbSi 2 ), molybdenum silicide (MoSi 2 ), vanadium silicide (VSi 2 ),
Silicides such as tungsten silicide (WSi 2 ), magnesium silicide (Mg 2 Si), nickel silicide (Ni 3 Si 2 ), cobalt silicide (CoSi 2 ), manganese silicide (MnSi), and beryllium silicide (BeSi 2 ); and boron Titanium boride (TiB 2 ), zirconium boride (ZrB), chromium boride (CrB 2 ), hafnium boride (HfB 2 ), tantalum boride (TaB 2 ), niobium boride (NbB 2 ), molybdenum boride ( Examples include borides such as MoB 2 ), vanadium boride (VB 2 ), and tungsten boride (WB), and one or more borides selected from the group consisting of these are used. All of these compounds have the function of promoting sintering of the sintered body, and improve the wettability of the main component, Si 3 N 4 , making the sintered body denser and shortening the sintering time. This also causes a decrease in the sintering temperature. These substances are used in a total amount of 0.05 to 5% by weight, preferably 0.1 to 3% by weight.
If the amount of these substances added is less than 0.05% by weight, the effect of the addition will not be sufficient, while if it exceeds 5% by weight, the high temperature strength of the resulting sintered body will be impaired. Mixing of powders having the above-mentioned amounts is usually done by
The method used for the mixing operation may be used, e.g.
This can be carried out using a grinding mixer such as a ball mill, and by adding a solvent such as n-butyl alcohol as necessary. Next, a binder such as paraffin is preferably added to the mixed powder thus prepared, and an appropriate pressure is applied to form a compact into a predetermined shape. In addition, if a binder is added, the temperature will be 600 to 800℃.
It is preferable to perform heat treatment to volatilize and remove the binder before sintering. Furthermore, a sintered body is obtained by sintering this molded body in a non-oxidizing atmosphere. Sintering is
For example, 1500-1900℃, preferably 1600-1800℃
This can be done by heating. Examples of the non-oxidizing atmosphere include nitrogen, argon, and the like. In an oxidizing atmosphere, Si 3 N 4 is oxidized to form SiO 2
This is not possible because Incidentally, during this sintering, sintering may be performed in a hot press state where a pressure of 50 to 500 kg/cm 2 is applied, or in a pressurized state in a non-oxidizing gas atmosphere. Alternatively, even if sintering is performed in a pressurized atmosphere after sintering by a normal sintering method, the characteristics of the sintered body according to the present invention will not be impaired in any way. . The present invention will be explained in more detail below with reference to Examples and Reference Examples. Examples 1-12 Average particle size containing 85% alpha-phase silicon nitride
By heating 1.2μ silicon nitride powder at 1650℃ for 1 hour in a nitrogen atmosphere,
Silicon nitride powder with reduced oxygen and silicon oxide concentrations was obtained. Such silicon nitride powder, Y2O3 powder with average particle size 1μ, Al2O3 powder with average particle size 0.5μ , average particle size 1.5μ
AlN powder and TiO 2 , ZrO 2 with an average particle size of 1μ,
Cr2O3 , HfO2 , Ta2O5 , Nb2O5 , MoO3 , V2O5 ,
WO3 , NiO, CoO, MnO2 , BeO, TiC, TiSi2 ,
Using each powder of TiB, 12 types of mixed powders were prepared with the blending amounts (wt%) shown in the table. Each of the mixed powders was pulverized and mixed for 24 hours using a rubber lined ball mill using n-butyl alcohol as a solvent. 7% by weight of paraffin was added as a binder to the raw material powder prepared in this way, and a molding pressure of 700 kg/cm 2 was applied to the raw material powder, and the length was 60 mm.
A plate-shaped molded body having a width of 40 mm and a thickness of 10 mm was produced. The molded bodies were first heat-treated at 700°C to volatilize and remove the binder, and then sintered at 1750°C in a nitrogen gas atmosphere to obtain silicon nitride ceramic sintered bodies. Reference Examples 1 to 10 Use silicon nitride powder without heat treatment, or use Si 3 N 4 powder, Y 2 O 3 powder, Al 2 O 3 powder, AlN powder, and powder added as the fifth component. Ten types of sintered bodies having the compositions shown in the table were prepared in the same manner as in the examples except that the blending amounts were changed. The relative density and bending strength (mechanical strength) of each sintered body obtained by the above procedure were measured, and the results are also listed in the table. Note that the relative density in the table is a relative value (%) based on the theoretical density. In addition, the bending strength value is based on a 3-point bending strength test, and the sample size is 3×
3 x 30 (mm), test condition is crosshead speed
0.5mm/min, span 20mm, temperature is room temperature and 1300℃
All measurements at each temperature were performed four times, and the average value is listed.
【表】【table】
【表】
表から明らかなように、本発明方法により得ら
れた焼結体は、普通焼結法により得たものである
にも拘らず、相対密度が98％以上で、抗折強度が
常温で80Kg／mm2以上、1300℃で55Kg／mm2以上とい
う優れた特性を有するものであることが確認され
た。
又、上記実施例の他に、前記熱処理を施した
Si3N4粉末86重量％、Y2O3粉末５重量％、Al2O3
粉末3.5重量％、AlN粉末3.5重量％、並びに第５
成分として、ZrC、Cr3C2、HfC、TaC、NbC、
Mo2C、VC、WC、B4C、ZrSi2、CrSi2、HfSi2、
TaSi2、NbSi2、MoSi2、VSi2、WSi2、Mg2Si、
Ni3Si2、CoSi2、MnSi、BeSi2、ZrB、CrB2、
HfB2、TaB2、NbB2、MoB2、VB2及びWBから
成る群より選ばれた１種もしくは２種以上のもの
を２重量％加えて成る組成のものを、実施例と同
様の操作により調製し、焼結体を得た。これら焼
結体についても同様に、相対密度及び抗折強度を
測定したところ、実施例と同様の結果が得られ
た。
発明の効果
本発明のセラミツクス焼結体の製造方法によれ
ば、高密度で、高温時における機械的強度の低下
度合が少ないセラミツクス焼結体が得られるもの
であり、又、本発明の製造方法は加圧を要しない
ので大量生産に適したものであり、工業上大変有
利なものである。[Table] As is clear from the table, the sintered body obtained by the method of the present invention has a relative density of 98% or more and a bending strength at room temperature, although it was obtained by the ordinary sintering method. It was confirmed that it has excellent properties of 80 Kg/mm 2 or more at temperature and 55 Kg/mm 2 or more at 1300°C. In addition to the above examples, the above heat treatment was performed.
Si 3 N 4 powder 86% by weight, Y 2 O 3 powder 5% by weight, Al 2 O 3
3.5% by weight of powder, 3.5% by weight of AlN powder, and 5th
Ingredients include ZrC, Cr 3 C 2 , HfC, TaC, NbC,
Mo2C , VC, WC, B4C , ZrSi2 , CrSi2 , HfSi2 ,
TaSi 2 , NbSi 2 , MoSi 2 , VSi 2 , WSi 2 , Mg 2 Si,
Ni3Si2 , CoSi2 , MnSi, BeSi2 , ZrB , CrB2 ,
A composition containing 2% by weight of one or more selected from the group consisting of HfB 2 , TaB 2 , NbB 2 , MoB 2 , VB 2 and WB was prepared in the same manner as in the example. A sintered body was obtained. When the relative density and bending strength of these sintered bodies were similarly measured, the same results as in the examples were obtained. Effects of the Invention According to the method for manufacturing a ceramic sintered body of the present invention, a ceramic sintered body with high density and less decrease in mechanical strength at high temperatures can be obtained, and the manufacturing method of the present invention Since it does not require pressurization, it is suitable for mass production and is very advantageous industrially.
Claims (1)
化ケイ素粉末75重量％以上：少なくとも１種以上
の稀土類元素の酸化物粉末0.1〜10重量％：酸化
アルミニウム粉末0.1〜10重量％：窒化アルミニ
ウム粉末0.1〜10重量％：並びにチタン、ジルコ
ニウム、クロム、ハフニウム、タンタル、ニオ
ブ、モリブデン、バナジウム及びタングステンの
それぞれの酸化物、炭化物、珪化物及び硼化物；
マグネシウム、ニツケル、コバルト、マンガン及
びベリリウムのそれぞれの酸化物及び珪化物；及
び炭化硼素から成る群より選ばれた１種もしくは
２種以上の粉末0.05〜５重量％から成る混合粉末
を成形し、該成形体を非酸化性雰囲気中において
焼結することを特徴とするセラミツクス焼結体の
製造方法。1 75% by weight or more of silicon nitride powder heat-treated in a non-oxidizing atmosphere: 0.1-10% by weight of oxide powder of at least one rare earth element: 0.1-10% by weight of aluminum oxide powder: 0.1% by weight of aluminum nitride powder ~10% by weight: and respective oxides, carbides, silicides and borides of titanium, zirconium, chromium, hafnium, tantalum, niobium, molybdenum, vanadium and tungsten;
A mixed powder consisting of 0.05 to 5% by weight of one or more powders selected from the group consisting of oxides and silicides of magnesium, nickel, cobalt, manganese and beryllium; and boron carbide is molded. A method for producing a ceramic sintered body, which comprises sintering a molded body in a non-oxidizing atmosphere.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56192364A JPS5895655A (en) | 1981-11-30 | 1981-11-30 | Manufacture of ceramic sintered body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56192364A JPS5895655A (en) | 1981-11-30 | 1981-11-30 | Manufacture of ceramic sintered body |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5895655A JPS5895655A (en) | 1983-06-07 |
| JPH0247426B2 true JPH0247426B2 (en) | 1990-10-19 |
Family
ID=16290046
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56192364A Granted JPS5895655A (en) | 1981-11-30 | 1981-11-30 | Manufacture of ceramic sintered body |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5895655A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6051668A (en) * | 1983-07-29 | 1985-03-23 | 株式会社東芝 | Antiabrasive member |
| US5178647A (en) * | 1983-07-29 | 1993-01-12 | Kabushiki Kaisha Toshiba | Wear-resistant member |
| JPS6178657A (en) * | 1984-09-27 | 1986-04-22 | Toshiba Corp | Guide member for printer |
| JPS62278169A (en) * | 1986-05-26 | 1987-12-03 | 東芝タンガロイ株式会社 | Ceramic sintered body parts and manufacture |
| JPS63218584A (en) * | 1987-03-05 | 1988-09-12 | 株式会社東芝 | Ceramic sintered body |
-
1981
- 1981-11-30 JP JP56192364A patent/JPS5895655A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5895655A (en) | 1983-06-07 |
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