WO2011001656A1 - スパークプラグ及びスパークプラグの製造方法 - Google Patents
スパークプラグ及びスパークプラグの製造方法 Download PDFInfo
- Publication number
- WO2011001656A1 WO2011001656A1 PCT/JP2010/004263 JP2010004263W WO2011001656A1 WO 2011001656 A1 WO2011001656 A1 WO 2011001656A1 JP 2010004263 W JP2010004263 W JP 2010004263W WO 2011001656 A1 WO2011001656 A1 WO 2011001656A1
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- WIPO (PCT)
- Prior art keywords
- component
- alumina
- sintered body
- spark plug
- insulator
- Prior art date
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- 238000000034 method Methods 0.000 title claims description 19
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 122
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 87
- 239000012212 insulator Substances 0.000 claims abstract description 60
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 36
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 36
- 239000013078 crystal Substances 0.000 claims abstract description 29
- 239000011521 glass Substances 0.000 claims abstract description 24
- 229910052751 metal Inorganic materials 0.000 claims abstract description 23
- 239000002184 metal Substances 0.000 claims abstract description 23
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 16
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000010703 silicon Substances 0.000 claims abstract description 5
- 238000010304 firing Methods 0.000 claims description 35
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 32
- 239000002245 particle Substances 0.000 claims description 32
- 238000004458 analytical method Methods 0.000 claims description 23
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 239000002585 base Substances 0.000 claims description 11
- 230000000737 periodic effect Effects 0.000 claims description 7
- 230000005540 biological transmission Effects 0.000 claims description 5
- 230000007704 transition Effects 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 68
- 239000012071 phase Substances 0.000 description 66
- 239000002994 raw material Substances 0.000 description 27
- 150000001875 compounds Chemical class 0.000 description 23
- 239000000463 material Substances 0.000 description 12
- 239000011777 magnesium Substances 0.000 description 11
- 238000005245 sintering Methods 0.000 description 10
- 238000002844 melting Methods 0.000 description 9
- 239000011575 calcium Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 7
- 230000015556 catabolic process Effects 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 238000002485 combustion reaction Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 238000004445 quantitative analysis Methods 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- 230000002159 abnormal effect Effects 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 229910052573 porcelain Inorganic materials 0.000 description 4
- 230000035939 shock Effects 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 229910052788 barium Inorganic materials 0.000 description 3
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 3
- 150000001805 chlorine compounds Chemical class 0.000 description 3
- 238000004453 electron probe microanalysis Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000004679 hydroxides Chemical class 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 150000002823 nitrates Chemical class 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 239000000395 magnesium oxide Substances 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
- 229910052759 nickel Inorganic materials 0.000 description 2
- -1 oxides Substances 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910001209 Low-carbon steel 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
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052773 Promethium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 241000978776 Senegalia senegal Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 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
- 235000010489 acacia gum Nutrition 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000004323 axial length Effects 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 229910052730 francium Inorganic materials 0.000 description 1
- KLMCZVJOEAUDNE-UHFFFAOYSA-N francium atom Chemical compound [Fr] KLMCZVJOEAUDNE-UHFFFAOYSA-N 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 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
- 238000007561 laser diffraction method Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 239000005445 natural material Substances 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- UZLYXNNZYFBAQO-UHFFFAOYSA-N oxygen(2-);ytterbium(3+) Chemical compound [O-2].[O-2].[O-2].[Yb+3].[Yb+3] UZLYXNNZYFBAQO-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010959 steel Substances 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
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- FRNOGLGSGLTDKL-UHFFFAOYSA-N thulium atom Chemical compound [Tm] FRNOGLGSGLTDKL-UHFFFAOYSA-N 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- 229910003454 ytterbium oxide Inorganic materials 0.000 description 1
- 229940075624 ytterbium oxide Drugs 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01T—SPARK GAPS; OVERVOLTAGE ARRESTERS USING SPARK GAPS; SPARKING PLUGS; CORONA DEVICES; GENERATING IONS TO BE INTRODUCED INTO NON-ENCLOSED GASES
- H01T13/00—Sparking plugs
- H01T13/20—Sparking plugs characterised by features of the electrodes or insulation
- H01T13/38—Selection of materials for insulation
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
- C04B35/111—Fine ceramics
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
- C04B35/111—Fine ceramics
- C04B35/117—Composites
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/62695—Granulation or pelletising
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/64—Burning or sintering processes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01T—SPARK GAPS; OVERVOLTAGE ARRESTERS USING SPARK GAPS; SPARKING PLUGS; CORONA DEVICES; GENERATING IONS TO BE INTRODUCED INTO NON-ENCLOSED GASES
- H01T21/00—Apparatus or processes specially adapted for the manufacture or maintenance of spark gaps or sparking plugs
- H01T21/02—Apparatus or processes specially adapted for the manufacture or maintenance of spark gaps or sparking plugs of sparking plugs
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3201—Alkali metal oxides or oxide-forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
-
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Definitions
- the present invention relates to a spark plug and a method for manufacturing the spark plug, and more particularly to a spark plug that achieves a high withstand voltage characteristic at a high temperature and that does not easily deteriorate at a high temperature, and a method for manufacturing the spark plug.
- Patent Document 1 "Y 2 O 3, ZrO 2, La 2 O 3 , at least one additive was more chosen, or selected from Y 2 O 3, ZrO 2, La 2 O 3
- a highly insulating high-alumina porcelain composition using a mixed raw material powder composed of at least one additive and a solid solution composite oxide of alumina and an alumina fine-grained powder having a particle size of 0.5 ⁇ m or less is described. (See claim 1 of Patent Document 1).
- Al 2 O 3 alumina having an average particle diameter of 1 ⁇ m or less, yttria (Y 2 O 3 ), magnesia (MgO), zirconia formed in a grain boundary phase. (ZrO 2 ) and at least one of compounds and mixtures of Al 2 O 3 with at least one of lanthanum oxide (La 2 O 3 ) and a porosity of 6% by volume or less ” (See claim 1 of Patent Document 2).
- the “high voltage endurance alumina-based sintered body” according to Patent Document 3 describes “the content of each of the Si component, Ca component, and Mg component contained in 100 parts by weight of the alumina-based sintered body in terms of oxides. (Unit: part by weight), C (unit: part by weight), and M (unit: part by weight), the contents of the above three components satisfy the following relational expression, and mullite (Al 6 Si 2 O 13 ) having at least a crystal phase ... 0.95 ⁇ S / (S + C + M) ⁇ 0.75 ”(see claim 1 of Patent Document 3).
- Patent Document 4 states that “a sintered body of rare earth oxide 5 to 95 wt%, alumina 94.9 to 4.9 wt% and silica 0.1 to 10 wt%, and that the crystal grain size of the sintered body is 30 ⁇ m or less. A characteristic rare earth oxide-alumina-silica sintered body is described (see claim 1 of Patent Document 4).
- Patent Document 5 states that “the total component is 100% by mass, the Al component is 95 to 99.8% by mass, and the rare earth element and the Si component are rare earth elements (R RE ). And the Si component (R si / R si ) ratio (R RE / R si ) is 0.1 to 1.0, and the maximum length per 1 mm 2 of the cut surface is 10 ⁇ m or more. Further, it is described as “insulator for spark plug, wherein the number of alumina particles having an aspect ratio of 3 or more is less than 10” (see claim 1 of Patent Document 5).
- Patent Document 6 states that “alumina-based porcelain composition containing alumina as a main component, the alumina as the main component, and a composition of at least one element selected from Al, Si, Mg, and rare earth elements; When the alumina as the main component is 100 parts by weight, the composition of at least one element selected from Al, Si, Mg and rare earth elements is 5 parts by weight or less. It is described as “alumina porcelain composition characterized by this” (see claim 1 of Patent Document 6).
- the spark plug for an internal combustion engine described in Patent Document 7 is composed of “one or two or more selected from Si, Ca, Mg, Ba and B components as components other than the alumina component.
- the content of the additive element-based powder is the total content of each component in terms of oxide, and should be blended within the range of 4 to 7% by mass.
- each additive element powder for example, Si component is SiO 2 powder, Ca component is CaCO 3 powder, Mg component is MgO powder, Ba component is BaCO 3 powder, and B component is H 3 BO 3 powder (or aqueous solution may be used) ⁇ ⁇ Si, Ca, Mg and Ba components in the additive element powders, in addition to oxides, hydroxides, carbonates, chlorides, sulfates, nitrates and phosphorus It is also possible to use various inorganic raw material powders such as acid salts. " (Refer to column 0055).
- the spark plug has much higher withstand voltage characteristics, particularly, more excellent withstand voltage characteristics at high temperatures at which dielectric breakdown easily occurs, and further withstand voltage characteristics at high temperatures. Therefore, there has been a demand for a spark plug that is difficult to decrease and an efficient manufacturing method of the spark plug.
- the problem to be solved by the present invention is to provide a spark plug provided with an insulator that achieves high withstand voltage characteristics at high temperatures and that does not easily lower the withstand voltage characteristics at high temperatures.
- Another problem to be solved by the present invention is to provide a spark plug having an insulator exhibiting high withstand voltage characteristics at high temperatures while maintaining thermal shock and sinterability.
- Still another problem to be solved by the present invention is to provide a spark plug including an insulator that exhibits high withstand voltage characteristics at high temperatures and is resistant to high temperature leakage while maintaining thermal shock and / or sinterability. That is.
- Another problem to be solved by the present invention is to provide a spark plug manufacturing method capable of efficiently manufacturing the spark plug.
- a spark plug comprising a center electrode, a substantially cylindrical insulator provided on the outer periphery of the center electrode, and a substantially cylindrical metal shell provided on the outer periphery of the insulator,
- the insulator includes an alumina containing a silicon component (hereinafter referred to as an Si component), a Group 2 element component of the periodic table based on the IUPAC 1990 recommendation, and a rare earth element component (hereinafter referred to as an RE component).
- the alumina-based sintered body consists of a glass phase and an alumina crystal phase as a result of analysis by X-ray diffraction,
- the grain boundary phase of the alumina-based sintered body was observed with a transmission electron microscope, and the mass ratio [alkali metal / RE] in terms of oxide of the alkali metal component and the RE component in a circular spot having a diameter of 0.3 nm was determined.
- the average value of the mass ratios of the 30 spots calculated and arbitrarily selected in the observation region is either 0.01 or more and 0.45 or less, and 0.45 or more and 1.0 or less.
- Spark plug characterized by being in the range of (2)
- the spark plug according to (1) wherein a mass ratio in terms of oxide of the RE component and the Si component contained in the alumina-based sintered body satisfies 0.45 ⁇ RE / SiO 2 ⁇ 1.2, (3)
- the mass ratio in terms of oxides of the SiO 2 component, the SiO 2 component, and the Group 2 element component contained in the alumina-based sintered body is 0.2 ⁇ SiO 2 / (SiO 2 +2 group) ⁇
- the spark plug according to (1) or (2) which satisfies 0.75
- the average particle diameter of the alumina particles contained in the alumina-based sintered body is 2.5 to 6 ⁇ m
- the sparking step is characterized in that the temperature is raised from 900 ° C. to the firing temperature at an average heating rate of 8 to 20 ° C./min, and the firing temperature is maintained within a temperature range of 1510 to 1650 ° C.
- a manufacturing method of a plug can be mentioned.
- a spark plug including an insulator that achieves a high withstand voltage characteristic at a high temperature and further has a low withstand voltage characteristic at a high temperature.
- a spark plug including an insulator that exhibits high withstand voltage characteristics at high temperatures while maintaining thermal shock and sinterability.
- a spark plug including an insulator that exhibits high withstand voltage characteristics at high temperatures and does not leak at high temperatures while maintaining thermal shock and / or sinterability.
- FIG. 1 is an explanatory view showing an embodiment of a spark plug according to the present invention
- FIG. 1 (a) is a partial cross-sectional explanatory view showing the spark plug according to the embodiment
- FIG. FIG. 3 is a cross-sectional explanatory view showing a tip portion of the spark plug.
- FIG. 2 shows an example of an apparatus for measuring a withstand voltage characteristic of an insulator in a spark plug according to the present invention at a high temperature
- FIG. 2A is an overhead view of a sintered body and a metal ring.
- FIG. 2B is a cross-sectional view of the sintered body and the ring.
- a spark plug according to the present invention includes a center electrode, a substantially cylindrical insulator provided on the outer periphery of the center electrode, and a substantially cylindrical metal shell provided on the outer periphery of the insulator.
- the insulator includes a silicon component (hereinafter referred to as Si component), a Group 2 element component of the periodic table based on the IUPAC 1990 recommendation, and a rare earth element component (hereinafter referred to as RE component).
- the alumina-based sintered body comprises a glass phase and an alumina crystal phase as a result of analysis by X-ray diffraction, and transmits the grain boundary phase of the alumina-based sintered body.
- the average value of the mass ratio of the 30 selected spots is in the range of 0.01 or more and 0.45 or less and in the range of 0.45 or more and 1.0 or less, that is, 0 It is characterized by being in the range of .01 to 1.0.
- the alumina-based sintered body includes a Si component, a Group 2 element component of the periodic table based on the IUPAC 1990 recommendation (hereinafter sometimes simply referred to as “Group 2 component”), a RE component, and most of them. And an alkali component as an inevitable impurity.
- the Al component is mostly aluminum oxide (Al 2 O 3 ), that is, alumina, and is contained in the alumina-based sintered body.
- the content of the Al component is preferably in the range of 85 to 96% by mass in terms of oxide when the alumina-based sintered body after firing is 100% by mass.
- the content of the Al component is 85 to 96% by mass in terms of oxide, the withstand voltage characteristic of the insulator in the spark plug according to the present invention can be maintained at a high level.
- the Si component is a component derived from a sintering aid and is present in the alumina-based sintered body as an oxide or an ion.
- the Si component melts during sintering and usually generates a liquid phase, and thus functions as a sintering aid that promotes densification of the sintered body.
- the Si component often forms a low-melting glass phase or the like in the grain boundary phase of alumina crystal particles after sintering.
- the Si component is not only a low-melting glass phase but also a high-melting glass phase or the like. Is easily formed with priority. Therefore, the alumina-based sintered body is difficult to melt at a low temperature, and thus migration or the like that can cause dielectric breakdown is unlikely to occur.
- Examples of the raw material of the Si component include silicon oxide and a compound that is converted into the Si component by firing.
- Examples of the compound to be converted into the Si component include various inorganic powders such as silicon oxide, composite oxide, hydroxide, carbonate, chloride, sulfate, nitrate, and phosphate, and natural minerals. Etc. Specifically, mention may be made of SiO 2 powder or the like as a preferable compound powder.
- the usage-amount shall be the oxide conversion mass% when converted into an oxide.
- the purity and average particle diameter of the raw material powder of the Si component are basically the same as those of the compound powder that can be the Al component.
- the Group 2 component contained in the alumina-based sintered body is a component derived from a sintering aid.
- the Group 2 component may be a compound containing a Group 2 element of the periodic table based on the IUPAC 1990 recommendation.
- the Group 2 component is present in the alumina-based sintered body as an oxide, ion, or the like, and functions as a sintering aid during sintering, like the Si component.
- examples of the Group 2 component include a magnesium component (hereinafter sometimes referred to as an Mg component) such as magnesium oxide, and a calcium component (hereinafter sometimes referred to as a Ca component) such as calcium oxide.
- the alumina-based sintered body in the spark plug according to the present invention only needs to contain one or more of the group 2 components. It is preferable that the alumina-based sintered body contains a Group 2 component because the high-temperature strength of the resulting alumina-based sintered body can be improved. More preferably, an aspect in which the alumina-based sintered body includes two or more types of the Group 2 components can be exemplified, and an aspect in which the alumina-based sintered body includes three or more types of the Group 2 components is particularly preferable. be able to.
- the raw material for the Group 2 component is not particularly limited as long as it is an oxide of a Group 2 element that is a Group 2 component and a compound that can become a Group 2 component by firing.
- Examples include Group 2 element oxides, composite oxides, hydroxides, carbonates, chlorides, sulfates, nitrates, and various inorganic powders such as phosphates, and natural minerals.
- examples of the Ca compound powder include CaO powder and CaCO 3 powder
- examples of the Ba compound powder include BaO powder and BaCO 3 powder.
- the usage-amount of the powder is the oxide conversion mass% when converted into an oxide.
- the content of the Group 2 components is the sum of the contents of the Group 2 components.
- the purity and average particle size of the Group 2 component powder are basically the same as those of the compound powder that can be an Al component.
- the RE component is a component derived from a sintering aid and is present in the alumina-based sintered body as an oxide, an ion, or the like.
- the RE component include scandium components (hereinafter sometimes referred to as Sc components), yttrium components (hereinafter sometimes referred to as Y components), such as yttrium oxide and lanthanoid components.
- Specific examples of the RE component contained in the alumina-based sintered body include an Sc component, a Y component, a lanthanum component (hereinafter sometimes referred to as a La component), such as an oxide of lanthanum, a cerium component (hereinafter referred to as a Ce component).
- Pr component Praseodymium component
- Nd component neodymium component
- Pm component promethium component
- Sm component samarium component
- Eu component europium component
- Gd component gadolinium component
- Tb component Terbium component
- Dysprosium component hereinafter sometimes referred to as Dy component
- Ho component holmium component
- Er component erbium component
- Tm components Thulium components
- Yb components ytterbium components
- Lu components ytterbium oxide and lutetium components
- Etc. Preferred examples of the RE component include La component, Nd component, Pr component, Y component, and Yb component.
- La component, Nd component, Pr component, Y component and Yb component have a small ionic radius and are easily dispersed uniformly in the alumina-based sintered body together with the Si component. It is thought that can be formed.
- the RE component is contained in the alumina-based sintered body at the time of sintering, thereby suppressing excessive grain growth of alumina at the time of sintering and forming a glass phase in the grain boundary phase together with the Si component. Since the glass phase formed in the grain boundary phase has a high melting point, it can improve the withstand voltage characteristics of the alumina-based sintered body at a high temperature and can also improve the high-temperature strength of the alumina-based sintered body. .
- the raw material for the RE component is not particularly limited as long as it is an oxide of RE, which is the RE component, or a compound that is converted to the RE component by firing.
- the compound that is converted to the RE component upon firing include various inorganic powders such as oxides, composite oxides, hydroxides, carbonates, chlorides, sulfates, nitrates, and phosphates of RE elements, and natural substances.
- a mineral etc. can be mentioned.
- the content of the RE component contained in the alumina-based sintered body is an oxide equivalent mass% when the RE component is converted into an oxide.
- content of RE component Pr component adopts oxide equivalent mass% when converted to “Pr 6 O 11 ”, and RE component other than Pr component when converted to “RE 2 O 3 ” Oxide equivalent mass% is adopted.
- the RE component content is the sum of the content of each RE component.
- the amount used is an oxide equivalent mass% when a compound other than the oxide to be used is converted into an oxide.
- the purity and average particle size of the RE component raw material powder are basically the same as those of the compound powder that can be an Al component. Further, the purity and average particle size of the RE component compound powder are basically the same as those of the compound powder that can be the Al component.
- the contents of the Al component, the Si component, the Group 2 component, and the RE component contained in the alumina-based sintered body are, for example, fluorescent X-ray analysis, chemical analysis, or It can be measured by quantitative analysis using an electron beam microanalyzer (EPMA), and the mass% in terms of oxide can be calculated.
- EPMA electron beam microanalyzer
- the result calculated by subjecting the alumina-based sintered body to fluorescent X-ray analysis or chemical analysis almost coincides with the mixing ratio of the raw material powders.
- the alumina-based sintered body is composed of a glass phase and alumina crystals as a result of analysis by X-ray diffraction. That is, there is no crystal phase at a level detected by X-ray diffraction in the grain boundary phase present in the alumina-based sintered body. Note that “there is no crystal phase at a level detected by X-ray diffraction” means that the intensity ratio between the strongest peak derived from alumina obtained by X-ray diffraction and the strongest peak derived from a crystal phase other than alumina [crystal phase / Alumina] is 0 or more and 0.05 or less.
- X-ray diffraction uses, for example, MiniFlex manufactured by Rigaku Corporation, and the measurement is performed under the conditions of a measurement angle range of 20 to 70 °, a voltage value of 30 kV, a current value of 15 mA, a scan speed of 1, and a step of 0.02. It can be carried out.
- the BET specific surface area of the Si component raw material powder is usually adjusted to 30 to 45 m 2 / L, and the BET ratio of the Group 2 component raw material powder is adjusted.
- the mixture of these raw material powders is fired by adjusting the surface area to 28 to 40 m 2 / L and adjusting the ratio of the Group 2 component raw material powder / Si component raw material powder to 0.7 to 1.3. Is good.
- the specific surface area of the raw material powder is large, during firing, the raw material powder of the Si component and the raw material powder of the Group 2 component easily react, and as a result, a glass phase is formed, and alumina crystals are formed as the crystal phase. Generate.
- a crystal phase-forming substance other than the alumina crystal cannot be detected by X-ray diffraction.
- the RE component When the grain boundary phase present in the alumina-based sintered body has a crystal phase at a level detected by X-ray diffraction, the RE component is often unevenly dispersed in the alumina-based sintered body. . Since the RE component can block the conductive route, if the dispersion of the RE component is not uniform, the withstand voltage, particularly the withstand voltage at high temperatures, may vary. In addition, since the presence of the crystal phase itself causes the dielectric constant of the alumina-based sintered body to vary, the voltage application state is difficult to be uniform, and as a result, the withstand voltage varies.
- the crystal phase By firing the crystal phase present in the grain boundary phase at a high temperature, the crystal phase melts into the glass phase of the grain boundary phase. When the crystal phase melts, the components contained in the grain boundary phase are uniformly dispersed in the glass phase, so that the variation in withstand voltage is reduced.
- the alumina-based sintered body preferably does not contain a crystal phase in the grain boundary phase, as described above, the strongest peak derived from alumina obtained by X-ray diffraction and the strongest derived from a crystal phase other than alumina.
- the intensity ratio with respect to the peak [crystalline phase / alumina] is preferably 0 or more and 0.05 or less.
- alkali metal that is, a Group 1 element component of the periodic table based on the IUPAC 1990 recommendation.
- alkali metal examples include lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), and francium (Fr).
- Alkali metal is easy to move in the grain boundary phase. That is, the alkali metal tends to cause a dielectric breakdown of the alumina-based sintered body. However, if the alkali metal is contained in the high melting point glass phase, the alkali metal is difficult to move even at high temperatures. As a result, dielectric breakdown caused by movement of the alkali metal in the grain boundary phase is unlikely to occur, so that the withstand voltage characteristic at high temperature of the insulator in the spark plug according to the present invention is enhanced.
- the glass phase of the alumina-based sintered body contains an alkali metal, and further includes an RE component that blocks the conductive route, so that the insulator has high withstand voltage characteristics at high temperatures. Can be secured.
- an energy dispersive X-ray analyzer manufactured by EDAX
- TEM transmission electron microscope
- Examples thereof include a method of measuring by elemental analysis using EDX, model: Genesis 4000, detector: SUTW3.3 RTEM).
- Examples of the analysis conditions include an acceleration voltage of 200 kV, an irradiation mode of HR, a spot size of 0.3 nm, and observation of arbitrary 30 points on the glass phase present in the grain boundary phase. At each spot, the alkali metal content can be measured.
- the alkali metal and the RE component are contained in the alumina-based sintered body at a constant ratio. Therefore, an oxide-converted mass ratio, [alkali metal / RE], between the measured alkali metal content and the RE component content measured in advance by quantitative analysis using EPMA or the like is calculated.
- [alkali metal / RE] the mass ratio is calculated for every 30 spots in the TEM observation region, and the average value of the 30 mass ratios is adopted.
- the glass phase contains an appropriate amount of alkali metal and RE component. Become.
- the content of alkali metal in the glass phase of the alumina-based sintered body is preferably large, but if the average value of [alkali metal / RE] exceeds 0.2, the withstand voltage is not greatly affected.
- the mass ratio [alkali metal / RE] in the grain boundary phase of the alumina-based sintered body is 0.01 to 1.0, the insulator has excellent withstand voltage characteristics at high temperatures. Since the glass phase itself has a high melting point, the withstand voltage is hardly lowered even at high temperatures.
- the mass ratio of the RE component and the Si component in terms of oxide is 0.45 ⁇ RE / SiO 2 ⁇ 1.2, preferably 0.55 ⁇ RE / SiO 2.
- a spark plug including an alumina-based sintered body satisfying ⁇ 1 can be mentioned.
- RE / SiO 2 satisfies 0.45 to 1.2, the melting point of the grain boundary phase becomes high due to the high melting point of SiO 2 , so that the insulation of the insulator at high temperatures, for example, 850 ° C. and 900 ° C. Withstand voltage characteristics are improved.
- the mass ratio in terms of oxides of the SiO 2 component, the SiO 2 component, and the Group 2 element component is 0.2 ⁇ SiO 2 / (SiO 2 +2 group) ⁇
- a spark plug including an alumina-based sintered body that satisfies 0.75, preferably 0.25 ⁇ SiO 2 / (SiO 2 +2 group) ⁇ 0.7 can be given.
- SiO 2 / (SiO 2 +2 group) satisfies 0.2 to 0.75
- SiO 2 and Group 2 components form a eutectic composition, thereby suppressing abnormal grain growth that may occur due to firing. Therefore, the high temperature strength can be improved, and further, the dielectric strength characteristics of the insulator at high temperatures, for example, 850 ° C. and 900 ° C. can be secured.
- the average particle diameter of the alumina particles is there may be mentioned an embodiment in which 8 or more peaks derived from the RE component are observed when a line analysis is performed on an arbitrary part of the alumina-based sintered body over 180 ⁇ m.
- the surface of the sintered body is mirror-polished and the polished surface is subjected to thermal etching treatment for 10 minutes at a temperature 100 ° C. lower than the firing temperature.
- the surface which performed this process can be observed with a scanning electron microscope (SEM), and the method of measuring an average crystal grain diameter by the intercept method can be mentioned.
- SEM scanning electron microscope
- the surface of the sintered body is mirror-polished and the magnification of SEM is enlarged to about 700 times and observed with an energy dispersive X-ray analyzer (EDS).
- EDS energy dispersive X-ray analyzer
- An example is a method in which an arbitrary part of the sintered body is subjected to line analysis over 180 ⁇ m.
- Condition (1) When a line analysis by EDS is performed, the sintered body is capable of observing eight or more peaks derived from the RE component within 180 ⁇ m.
- Condition (2) The peak derived from the RE component has an intensity that is more than half that of the peak with the maximum intensity in the 180 ⁇ m line.
- Condition (3) In the valley existing between adjacent peaks, if the size of the valley seen from the weak peak side among the adjacent peaks is not 10% or more of the maximum intensity peak in the line, the adjacent peak Be one.
- a spark plug according to the present invention comprises a center electrode, a substantially cylindrical insulator provided on the outer periphery of the center electrode, and a ground electrode disposed so that one end faces the center electrode via a spark discharge gap. I have.
- the spark plug according to the present invention is a spark plug having such a configuration, other members and configurations are not particularly limited, and various known members and configurations can be adopted.
- FIG. 1 shows a spark plug as an embodiment of the spark plug according to the present invention.
- FIG. 1 (a) is a partial cross-sectional explanatory view of a spark plug 1 which is an embodiment of a spark plug according to the present invention
- FIG. 1 (b) is a spark which is an embodiment of a spark plug according to the present invention.
- 2 is an explanatory cross-sectional view showing the main part of the plug 1.
- FIG. 1A the lower side of the paper is the front end direction of the axis AX
- the upper side of the paper is the rear end direction of the axis AX
- FIG. 1B the upper side of the paper is the front side of the axis AX
- the lower side of the paper is the rear side of the axis AX. This will be described as the end direction.
- the spark plug 1 includes a substantially rod-shaped center electrode 2, a substantially cylindrical insulator 3 provided on the outer periphery of the center electrode 2, and an insulator 3. And a ground electrode 5 which is disposed so that one end thereof is opposed to the front end surface of the center electrode 2 via the spark discharge gap G and the other end is joined to the end surface of the metal shell 4. And.
- the metallic shell 4 has a cylindrical shape and is formed so as to hold the insulator 3 by incorporating the insulator 3 therein.
- a threaded portion 8 is formed on the outer peripheral surface in the front end direction of the metal shell 4, and the spark plug 1 is attached to a cylinder head (not shown) of the internal combustion engine using the threaded portion 8.
- the nominal diameter of the screw portion 8 is usually adjusted to 10 mm or less.
- the metal shell 4 can be formed of a conductive steel material, for example, low carbon steel.
- the center electrode 2 is formed of an outer member 6 and an inner member 7 formed so as to be concentrically embedded in an axial center portion inside the outer member 6.
- the center electrode 2 is fixed to the shaft hole of the insulator 3 with its tip portion protruding from the tip surface of the insulator 3, and is insulated and held with respect to the metal shell 4.
- the outer material 6 of the center electrode 2 is formed of a nickel-based alloy having excellent heat resistance and corrosion resistance
- the inner material 7 of the electrode 2 is formed of a metal material having excellent thermal conductivity such as copper (Cu) or nickel (Ni). Can be.
- the ground electrode 5 is formed in, for example, a prismatic body, one end is joined to the end face of the metal shell 4, is bent into an approximately L shape in the middle, and the tip is positioned in the direction of the axis AX of the center electrode 2. As such, its shape and structure are designed. By designing the ground electrode 5 in this way, one end of the ground electrode 5 is disposed so as to face the center electrode 2 with the spark discharge gap G interposed therebetween.
- the spark discharge gap G is a gap between the front end surface of the center electrode 2 and the surface of the ground electrode 5, and this spark discharge gap G is normally set to 0.3 to 1.5 mm. Since the ground electrode 5 is exposed to a higher temperature than the center electrode 2, the ground electrode 5 is preferably formed of a Ni-base alloy or the like that is more excellent in heat resistance and corrosion resistance than the Ni-base alloy that forms the center electrode 2.
- the insulator 3 is held on the inner peripheral portion of the metal shell 4 via talc and / or packing (not shown), and the center electrode 2 along the axis AX direction of the insulator 3. It has a shaft hole for holding.
- the insulator 3 is fixed to the metal shell 4 with the end of the insulator 3 in the tip direction protruding from the tip surface of the metal shell 4.
- the insulator 3 includes an alumina-based sintered material containing a silicon (Si) component, a Group 2 element component of the periodic table based on the IUPAC 1990 recommendation, and a rare earth element (RE) component as described above.
- the alumina-based sintered body has an intensity ratio [crystalline phase / alumina] of 0 to 0.05 inclusive, the strongest peak derived from alumina obtained by X-ray diffraction and the strongest peak derived from a crystal phase other than alumina.
- the grain boundary phase of the alumina-based sintered body was observed with a transmission electron microscope, and the mass ratio in terms of oxides of the alkali metal component and the RE component in a circular spot having a diameter of 0.3 nm [alkali metal / RE] is calculated, and the average value of the mass ratios of 30 spots arbitrarily selected in the observation region is 0.01 to 1.0. Since the compounds and physical properties contained in the insulator 3 have been described above, they may be omitted.
- raw material powder that is, powder of a compound that is converted into the Al component, the Si component, the Group 2 component, and the RE component by firing is mixed.
- each powder of the same material as the Al component, the same material as the Si component, the same material as the Group 2 component, and the same material as the RE component (these powders are also referred to as raw material powders). Can be referred to)).
- This mixing is preferably performed for 8 hours or more so that the mixed state of the raw material powders can be made uniform and the obtained sintered body can be highly densified.
- the particle size of the compound powder converted into the Al component, the Si component, the Mg component, the Group 2 component excluding the Mg component, and the RE component are included.
- the ratio of the particle size of the compound powder to be converted into the auxiliary material is 1.2 ⁇ alumina / auxiliary material ⁇ 4.4, the hexaaluminate phase is easily formed while ensuring good sinterability. This is preferable.
- the particle size of the powder is, for example, an average particle size measured by a laser diffraction method using a Microtrac particle size distribution measuring device (MT-3000) manufactured by Nikkiso Co., Ltd.
- a hydrophilic binder can be blended with the raw material powder as a binder.
- the hydrophilic binder include polyvinyl alcohol, water-soluble acrylic resin, gum arabic, and dextrin.
- distributes raw material powder water, alcohol, etc. can be used, for example.
- These hydrophilic binders and solvents can be used alone or in combination of two or more.
- the ratio of the hydrophilic binder and the solvent used is 0.1 to 7 parts by mass, preferably 1 to 5 parts by mass with respect to 100 parts by mass of the raw material powder. If water is used as the solvent, the amount can be 40 to 120 parts by mass, preferably 50 to 100 parts by mass.
- a slurry in which the raw material powder is dispersed can be obtained by dispersing the raw material powder in a solvent and blending a hydrophilic binder.
- the obtained slurry is spray-dried by a spray drying method or the like, and granulated to an average particle size of 30 to 200 ⁇ m, preferably 50 to 150 ⁇ m.
- the granulated product is molded to obtain a green molded body.
- the shape of the obtained green molded body is adjusted by grinding. Since the green compact is formed of a granulated product having a relatively large average particle size, it is excellent in processability and can be easily molded into a desired shape with high productivity.
- the green molded body that has been ground and molded into a desired shape is subjected to a baking step.
- the firing temperature is set to 1510 to 1650 ° C., more preferably 1550 to 1650 ° C. in the air atmosphere, and the temperature is raised from 900 ° C. to the firing temperature at an average temperature increase rate of 8 to 20 ° C./min. Firing for ⁇ 36 hours to obtain an alumina-based sintered body.
- the firing temperature is 1510 to 1650 ° C., the sintered body is easily densified sufficiently, the crystal phase is easily melted into the glass phase in the grain boundary phase, and abnormal grain growth of the alumina component is unlikely to occur.
- the withstand voltage characteristics and mechanical strength of the base sintered body can be ensured. If the average heating rate is less than 8 ° C./min, the glass phase that is the grain boundary phase becomes too low in melting point, which may cause abnormal grain growth of alumina particles and decrease strength.
- the firing temperature include a temperature within a temperature range of 1510 to 1650 ° C., and a temperature at which the temperature increase at the average temperature increase rate is stopped. This firing temperature is a temperature that is kept constant within the range of 1510 to 1650 ° C., and may vary within the above temperature range depending on circumstances. Further, if the firing time is 8 to 36 hours, the sintered body is easily densified sufficiently, and abnormal grain growth of the alumina component is unlikely to occur. Therefore, the withstand voltage characteristics and mechanical strength of the obtained alumina-based sintered body are improved. Can be secured.
- the obtained alumina-based sintered body is particularly suitable as the insulator 3 of the spark plug for an internal combustion engine with high output.
- the alumina-based sintered body may be shaped again if desired. In this manner, the alumina-based sintered body and the insulator 3 for the spark plug 1 made of the alumina-based sintered body can be produced.
- the obtained insulator 3 is subjected to a center electrode mounting step in which the center electrode 2 is assembled to the insulator 3.
- the spark plug 1 can be manufactured by being subjected to a metal shell attachment step of attaching the insulator 3 to which the center electrode 2 is assembled to the metal shell 4.
- a metal shell attachment step of attaching the insulator 3 to which the center electrode 2 is assembled to the metal shell 4.
- alumina powder having an average particle diameter of 2.1 ⁇ m, carbonate powder of SiO 2 powder, Mg component, Ca component, Sr component, Ba component, and rare earth element-containing powder were mixed. Furthermore, a hydrophilic binder such as polyvinyl alcohol and water as a solvent were added to prepare a molding base slurry.
- the obtained molding base slurry was spray-dried by a spray drying method or the like to prepare a spherical molding base granulated product. Further, the obtained green granulated material for molding was subjected to rubber press molding to produce a press-molded body serving as an original shape of the insulator.
- this press-molded body is cut on the outside with a resinoid grindstone or the like.
- this press-molded body was heated to 900 ° C. and then heated in the air atmosphere at an average temperature rising rate shown in Table 5.
- the firing time was 8 to 8 as shown in Table 5.
- the molded body was fired at 36 hours, and then subjected to finish firing with a glaze to obtain an insulator.
- Alkali metal content The content of alkali metal contained in the grain boundary phase of the sintered body is determined by the energy dispersive X-ray analyzer manufactured by EDAX, which is attached to the transmission electron microscope (TEM, model: HD-2000) manufactured by Hitachi, Ltd. It was measured by elemental analysis using (EDX, model: Genesis 4000, detector: SUTW3.3 RTEM). Analytical conditions are as follows: acceleration voltage is 200 kV, irradiation mode is HR, spot size is 0.3 nm, and any 30 points are observed at the site where the hexaaluminate phase and the glass phase present in the grain boundary phase react. It was set to the condition to do.
- the value obtained by calculating the average value of the observed 30 points of analysis results by mass% in terms of oxide was defined as the content of the alkali metal.
- the mass ratio between the alkali metal content of each sample and the RE component content obtained by quantitative analysis was calculated and shown in Table 2.
- samples “1 *” to “5 *” marked with “*” are comparative examples because the content ratio of “alkali metal / RE” is outside the range of 0.01 to 1.0. It is.
- FIG. 2A is a view of the sintered body 30 and a metal ring 31 that causes dielectric breakdown
- FIG. 2B is a cross-sectional view of the sintered body 30 and the ring 31. is there.
- the ring 31 has an axial length L of 3 to 4 mm, and is fixed in a non-contact state near the tip of the sintered body 30 by fixing means (not shown).
- One end of the sintered body 30 is fixed by the base 32, and the other end projects from the base 32.
- the portion protruding from the base 32 of the sintered body 30 is heated at a high frequency to 600 to 950 ° C., and the portion close to the metal ring 31 that is easily heated in the sintered body 30 is 800.
- the voltage value when reaching °C, 850 °C and 900 °C was measured as the withstand voltage value of the sample. Table 3 shows the measured withstand voltage values.
- the high temperature strength of the sintered body was measured by a method according to JIS R 1604 using a sample of 36 ⁇ 4 ⁇ 3 mm and setting the three-point bending strength to a span of 30 mm. Table 4 shows the measurement results.
- the particle size measurement of alumina was performed as follows. First, the surface of each sintered body was mirror-polished and subjected to thermal etching treatment for 10 minutes at a temperature 100 ° C. lower than the firing temperature. The surface subjected to this treatment was observed with a scanning electron microscope (SEM), and the average crystal grain size of the alumina particles was measured by the intercept method. The results are shown in Table 4.
- Line analysis The line analysis of the sintered body was performed as follows. The surface of each sintered body was mirror-polished, the magnification of SEM (model: JSM-6460LA) manufactured by JEOL Ltd. was increased to about 700 times, and the polished surface was observed. Line analysis was carried out over 180 ⁇ m of an arbitrary part of the sintered body according to (model: EX-23000BU). The applied voltage was set to 20 kV, and the intensity of the detected peak was determined based on the K ⁇ ray. Line analysis was performed at any seven locations where the sintered bodies were different, and the peaks derived from the detected RE component when four or more of the analysis results satisfied the following four locations were counted. Table 4 shows the number of peaks counted.
- Condition (1) When a line analysis by EDS is performed, the sintered body is capable of observing eight or more peaks derived from the RE component within 180 ⁇ m.
- Condition (2) The peak derived from the RE component has an intensity that is more than half that of the peak with the maximum intensity in the 180 ⁇ m line.
- Condition (3) In the valley existing between adjacent peaks, if the size of the valley seen from the weak peak side among the adjacent peaks is not 10% or more of the maximum intensity peak in the line, the adjacent peak Be one.
- Table 5 shows the firing temperature, firing time, and heating rate after 900 ° C. when each sample was produced. In addition, as for withstand voltage characteristics and high temperature strength evaluation, both Tables 3 and 4 are also shown.
- the insulator in the spark plug according to the present invention can be applied to a spark plug that can become high temperature during use, for example, a spark plug used in an internal combustion engine with high output.
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Abstract
Description
(1)中心電極と、前記中心電極の外周に設けられた略円筒状の絶縁体と、前記絶縁体の外周に設けられた略円筒状の主体金具とを備えたスパークプラグであって、
前記絶縁体は、ケイ素成分(以下においてSi成分と称する。)と、IUPAC1990年勧告に基づく周期表の第2族元素成分と、希土類元素成分(以下においてRE成分と称する。)とを含有するアルミナ基焼結体を備え、
前記アルミナ基焼結体は、X線回折により分析した結果としてガラス相とアルミナ結晶相とからなり、
前記アルミナ基焼結体の粒界相を、透過型電子顕微鏡で観察し、直径0.3nmの円形のスポットにおけるアルカリ金属成分及び前記RE成分の酸化物換算の質量比[アルカリ金属/RE]を算出し、観察領域中で任意に選択された30個の前記スポットの前記質量比の平均値が0.01以上0.45以下の範囲及び0.45を超え1.0以下の範囲のいずれかの範囲内にあることを特徴とするスパークプラグ、
(2)前記アルミナ基焼結体に含まれるRE成分とSi成分との酸化物換算での質量比が0.45≦RE/SiO2≦1.2を満たす(1)に記載のスパークプラグ、
(3)前記アルミナ基焼結体に含まれるSiO2成分とSiO2成分及び前記第2族元素成分との酸化物換算での質量比が0.2≦SiO2/(SiO2+2族)≦0.75を満たす(1)又は(2)に記載のスパークプラグ、
(4)前記アルミナ基焼結体に含まれるアルミナ粒子の平均粒径が2.5~6μmであり、
前記アルミナ基焼結体の任意の部位を180μmに亘ってライン分析したときに、RE成分由来のピークが8本以上観察される(1)~(3)のいずれか一つに記載のスパークプラグ、並びに
(5)(1)~(4)のいずれか一つに記載のスパークプラグを製造する方法であって、
未焼成成形体を焼成して絶縁体を形成する焼成工程と、
前記絶縁体に中心電極を組み付ける中心電極組付工程と、
前記中心電極が組み付けられた中心電極付き絶縁体を主体金具に取付ける主体金具取付工程とを備え、
前記焼成工程は、900℃から焼成温度まで平均昇温速度8~20℃/minで昇温し、前記焼成温度を1510~1650℃の温度範囲内に焼成温度を維持することを特徴とするスパークプラグの製造方法を挙げることができる。
ガラス相とアルミナ結晶とからなるアルミナ基焼結体を得るには、Si成分の原料粉末のBET比表面積を通常30~45m2/Lに調整するとともに、第2族成分の原料粉末のBET比表面積を28~40m2/Lに調整し、しかも、第2族成分の原料粉末/Si成分の原料粉末の比を0.7~1.3に調整してこれら原料粉末の混合物を焼成するのがよい。このように原料粉末の比表面積が大きいと、焼成時には、Si成分の原料粉末と第2族成分の原料粉末とが反応しやすくなり、その結果としてガラス相が形成され、結晶相としてアルミナ結晶が生成する。しかも、結晶相はX線回折で測定した限りでは、アルミナ結晶以外の結晶相形成物質はX線回折によっても検出することができないのである。
条件(1):EDSによるライン分析を行うと、180μmの間にRE成分由来のピークが8本以上観察することのできる焼結体であること。
条件(2):上記RE成分由来のピークが、180μmのライン中最大強度のピークに比べて、その半分以上の強度を有していること。
条件(3):隣接するピークの間に存在する谷において、隣接するピークのうち弱いピーク側からみた谷の大きさが、ライン中最大強度のピークの10%以上でない場合には、隣接するピークは1本とすること。
条件(4):ピーク強度は、ピークトップが示す強度から、ライン中最小強度の点が示す強度を差し引いた大きさとすること。
原料粉末として、平均粒径2.1μmのアルミナ粉末と、SiO2粉末、Mg成分、Ca成分、Sr成分、Ba成分の各炭酸塩粉末と、希土類元素含有粉末とを混合した。更に、親水性結合剤例えばポリビニルアルコールと、溶媒としての水とを添加して成形用素地スラリーを調製した。
得られた絶縁体の各成分の含有量は、EPMAを用いた定量分析により測定した。絶縁体に含まれる各成分の含有量は、表1に示す。
焼結体の粒界相に含まれるアルカリ金属の含有量は、株式会社日立製作所製の透過型電子顕微鏡(TEM、型式:HD-2000)に付属のEDAX社製のエネルギー分散型X線分析装置(EDX、型式:Genesis4000、検出器:SUTW3.3RTEM)を用いて元素分析することによって、測定した。分析の条件は、加速電圧が200kV、照射モードがHR、スポットサイズが0.3nm、ヘキサアルミネート相と粒界相に存在するガラス相とが反応している部位について、任意の30点を観察するという条件に設定した。この観察した30点の分析結果の平均値を酸化物換算の質量%で割り出した値を、前記アルカリ金属の含有量とした。各試料のアルカリ金属の含有量と、定量分析により得られたRE成分の含有量との質量比を算出し、表2に示した。
各試料の高温下における耐電圧を測定した。耐電圧を測定する装置を図2に示す。図2(a)は、焼結体30と、絶縁破壊を引き起こす金属製のリング31とを俯瞰した図であり、図2(b)は、焼結体30と前記リング31との断面図である。リング31は、その軸線長さLが3~4mmであり、図示しない固定手段によって、焼結体30の先端近傍に未接触状態で固定されている。焼結体30は、基部32により一端部が固定され、他端部が基部32から突出している。この高温下での耐電圧評価は、焼結体30の基部32から突出した部位を600~950℃に高周波加熱し、焼結体30における加熱され易い金属製のリング31に近接した部位が800℃、850℃及び900℃に達したときの電圧値を試料の耐電圧値として測定することとした。測定した耐電圧値を、表3に示す。
焼結体の高温強度の測定は、JIS R 1604に準拠した方法によって、36×4×3mmの大きさの試料を用いて3点曲げ強度をスパン30mmに設定して測定した。測定結果を表4に示す。
アルミナの粒径測定は、次のように行った。先ず、各焼結体の表面を鏡面研磨し、焼成温度よりも100℃低い温度で10分にわたって研磨面にサーマルエッチング処理を施した。この処理を施した表面を走査型電子顕微鏡(SEM)で観察し、インターセプト法にて、アルミナ粒子の平均結晶粒径を計測した。その結果を表4に示す。
焼結体のライン分析は、次のように行った。各焼結体の表面を鏡面研磨し、日本電子株式会社製のSEM(型式:JSM-6460LA)の倍率を700倍程度に拡大して研磨面を観察しつつ、日本電子株式会社製のEDX(型式:EX-23000BU)により焼結体の任意の部位を180μmに亘ってライン分析を行った。加圧電圧は20kVに設定し、検出されるピークの強度は、Kα線で元素を判別することとした。焼結体の異なる任意の7箇所においてライン分析を行い、その分析結果の4つ以上が次の4箇所の条件を満たす場合の検出されたRE成分由来のピークを計数した。計数したピーク数を表4に示す。
条件(1):EDSによるライン分析を行うと、180μmの間にRE成分由来のピークが8本以上観察することのできる焼結体であること。
条件(2):上記RE成分由来のピークが、180μmのライン中最大強度のピークに比べて、その半分以上の強度を有していること。
条件(3):隣接するピークの間に存在する谷において、隣接するピークのうち弱いピーク側からみた谷の大きさが、ライン中最大強度のピークの10%以上でない場合には、隣接するピークは1本とすること。
条件(4):ピーク強度は、ピークトップが示す強度から、ライン中最小強度の点が示す強度を差し引いた大きさとすること。
焼結体の高温リークの有無を確認した。詳しく言うと、所定の条件下で電圧を印加した後に、昇電圧負荷の状態になっている場合は高温リークが発生していると評価し、逆に昇電圧負荷の状態になっていない場合は高温リークが発生していないと評価した。上述の耐電圧評価と同一の装置を用いて、700℃、15kV、1時間という条件下において、高温リークの発生を検出することとした。高温リークの有無を表4に示し、高温リークが発生していた場合は「○」を示し、高温リークが発生していなかった場合は「×」を示した。
焼結体が緻密化されていることを確認するために、相対密度を算出した。各焼結体の相対密度は、先ずJIS R 1634に準拠した方法で見かけ密度を測定し、格子定数より算出した理論密度と測定した見かけ密度とを用いて算出した。算出した相対密度は、表4に示す。
2 中心電極
3 絶縁体
4 主体金具
5 接地電極
6 外材
7 内材
8 ネジ部
G 火花放電間隙
30 焼結体
31 リング
32 基部
L 軸線長さ
Claims (5)
- 中心電極と、前記中心電極の外周に設けられた略円筒状の絶縁体と、前記絶縁体の外周に設けられた略円筒状の主体金具とを備えたスパークプラグであって、
前記絶縁体は、ケイ素成分(以下においてSi成分と称する。)と、IUPAC1990年勧告に基づく周期表の第2族元素成分と、希土類元素成分(以下においてRE成分と称する。)とを含有するアルミナ基焼結体を備え、
前記アルミナ基焼結体は、X線回折により分析した結果としてガラス相とアルミナ結晶相とからなり、
前記アルミナ基焼結体の粒界相を、透過型電子顕微鏡で観察し、直径0.3nmの円形のスポットにおけるアルカリ金属成分及び前記RE成分の酸化物換算の重量比[アルカリ金属/RE]を算出し、観察領域中で任意に選択された30個の前記スポットの前記重量比の平均値が0.01以上0.45以下の範囲及び0.45を超え1.0以下の範囲のいずれかの範囲内にあることを特徴とするスパークプラグ。 - 前記アルミナ基焼結体に含まれるRE成分とSi成分との酸化物換算での質量比が0.45≦RE/SiO2≦1.2を満たす請求項1に記載のスパークプラグ。
- 前記アルミナ基焼結体に含まれるSiO2成分とSiO2成分及び前記第2族元素成分との酸化物換算での質量比が0.2≦SiO2/(SiO2+2族)≦0.75を満たす請求項1又は2に記載のスパークプラグ。
- 前記アルミナ基焼結体に含まれるアルミナ粒子の平均粒径が2.5~6μmであり、
前記アルミナ基焼結体の任意の部位を180μmに亘ってライン分析したときに、RE成分由来のピークが8本以上観察される請求項1~3のいずれか一項に記載のスパークプラグ1。 - 請求項1~4のいずれか一項に記載のスパークプラグを製造する方法であって、
未焼成成形体を焼成して絶縁体を形成する焼成工程と、
前記絶縁体に中心電極を組み付ける中心電極組付工程と、
前記中心電極が組み付けられた中心電極付き絶縁体を主体金具に取付ける主体金具取付工程とを備え、
前記焼成工程は、900℃から焼成温度まで平均昇温速度8~20℃/minで昇温し、前記焼成温度は1510~1650℃の温度範囲内に維持することを特徴とするスパークプラグの製造方法。
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