JP5172016B2 - 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
- JP5172016B2 JP5172016B2 JP2011520778A JP2011520778A JP5172016B2 JP 5172016 B2 JP5172016 B2 JP 5172016B2 JP 2011520778 A JP2011520778 A JP 2011520778A JP 2011520778 A JP2011520778 A JP 2011520778A JP 5172016 B2 JP5172016 B2 JP 5172016B2
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- Prior art keywords
- component
- alumina
- sintered body
- spark plug
- insulator
- Prior art date
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- 238000004519 manufacturing process Methods 0.000 title claims description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 118
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 84
- 239000012212 insulator Substances 0.000 claims description 58
- 229910052783 alkali metal Inorganic materials 0.000 claims description 34
- 150000001340 alkali metals Chemical class 0.000 claims description 34
- 238000010304 firing Methods 0.000 claims description 33
- 239000002245 particle Substances 0.000 claims description 33
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 32
- 239000013078 crystal Substances 0.000 claims description 28
- 239000011521 glass Substances 0.000 claims description 23
- 238000004458 analytical method Methods 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 18
- 238000002441 X-ray diffraction Methods 0.000 claims description 15
- 239000002585 base Substances 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 230000000737 periodic effect Effects 0.000 claims description 7
- 230000005540 biological transmission Effects 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 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
- 239000000203 mixture Substances 0.000 description 9
- 239000011575 calcium 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
- 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
- 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
Images
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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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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