CN101506117A - 用于固体氧化物燃料电池的玻璃陶瓷密封物 - Google Patents
用于固体氧化物燃料电池的玻璃陶瓷密封物 Download PDFInfo
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- CN101506117A CN101506117A CNA2007800175004A CN200780017500A CN101506117A CN 101506117 A CN101506117 A CN 101506117A CN A2007800175004 A CNA2007800175004 A CN A2007800175004A CN 200780017500 A CN200780017500 A CN 200780017500A CN 101506117 A CN101506117 A CN 101506117A
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- 239000002241 glass-ceramic Substances 0.000 title claims abstract description 112
- 239000000446 fuel Substances 0.000 title claims abstract description 23
- 239000007787 solid Substances 0.000 title claims abstract description 18
- 239000013078 crystal Substances 0.000 claims abstract description 64
- 239000011521 glass Substances 0.000 claims abstract description 55
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 16
- 229910052882 wollastonite Inorganic materials 0.000 claims abstract description 15
- 239000010456 wollastonite Substances 0.000 claims abstract description 15
- 239000006112 glass ceramic composition Substances 0.000 claims abstract description 14
- 238000007789 sealing Methods 0.000 claims abstract description 12
- 229910001462 kalsilite Inorganic materials 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims description 86
- 239000000463 material Substances 0.000 claims description 27
- 239000004615 ingredient Substances 0.000 claims description 22
- 229910052791 calcium Inorganic materials 0.000 claims description 19
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 12
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 11
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 11
- 229910052796 boron Inorganic materials 0.000 claims description 11
- 239000011777 magnesium Substances 0.000 claims description 11
- 239000011701 zinc Substances 0.000 claims description 11
- 229910052725 zinc Inorganic materials 0.000 claims description 11
- 229910052749 magnesium Inorganic materials 0.000 claims description 10
- 229910052788 barium Inorganic materials 0.000 claims description 9
- NWXHSRDXUJENGJ-UHFFFAOYSA-N calcium;magnesium;dioxido(oxo)silane Chemical compound [Mg+2].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O NWXHSRDXUJENGJ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052637 diopside Inorganic materials 0.000 claims description 8
- 229910052634 enstatite Inorganic materials 0.000 claims description 8
- 229910052839 forsterite Inorganic materials 0.000 claims description 8
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 claims description 8
- BBCCCLINBSELLX-UHFFFAOYSA-N magnesium;dihydroxy(oxo)silane Chemical compound [Mg+2].O[Si](O)=O BBCCCLINBSELLX-UHFFFAOYSA-N 0.000 claims description 8
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 6
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 6
- 229910001720 Åkermanite Inorganic materials 0.000 claims description 6
- 229910001678 gehlenite Inorganic materials 0.000 claims description 5
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 4
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 4
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- 239000010431 corundum Substances 0.000 claims description 4
- 239000010433 feldspar Substances 0.000 claims description 4
- -1 hardystonite Inorganic materials 0.000 claims description 4
- 239000004571 lime Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims 12
- 239000011575 calcium Substances 0.000 claims 7
- 239000011787 zinc oxide Substances 0.000 claims 6
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims 1
- 239000000919 ceramic Substances 0.000 abstract description 14
- 239000003795 chemical substances by application Substances 0.000 abstract description 9
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 229910020489 SiO3 Inorganic materials 0.000 abstract 1
- 210000004027 cell Anatomy 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 238000002425 crystallisation Methods 0.000 description 7
- 230000008025 crystallization Effects 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
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- 229910004762 CaSiO Inorganic materials 0.000 description 3
- SXQXMCWCWVCFPC-UHFFFAOYSA-N aluminum;potassium;dioxido(oxo)silane Chemical compound [Al+3].[K+].[O-][Si]([O-])=O.[O-][Si]([O-])=O SXQXMCWCWVCFPC-UHFFFAOYSA-N 0.000 description 3
- 239000004568 cement Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910016066 BaSi Inorganic materials 0.000 description 2
- 229910017639 MgSi Inorganic materials 0.000 description 2
- 229910004283 SiO 4 Inorganic materials 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052607 cyclosilicate Inorganic materials 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005382 thermal cycling Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910005793 GeO 2 Inorganic materials 0.000 description 1
- 229910017625 MgSiO Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 238000003279 ceramming Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
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- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000006064 precursor glass Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000007569 slipcasting Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Classifications
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- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0036—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/06—Other methods of shaping glass by sintering, e.g. by cold isostatic pressing of powders and subsequent sintering, by hot pressing of powders, by sintering slurries or dispersions not undergoing a liquid phase reaction
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0036—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents
- C03C10/0045—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents containing SiO2, Al2O3 and MgO as main constituents
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- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C29/00—Joining metals with the aid of glass
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- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
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- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
- C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc
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- 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
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C24/00—Coating starting from inorganic powder
- C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C24/00—Coating starting from inorganic powder
- C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
- C23C24/082—Coating starting from inorganic powder by application of heat or pressure and heat without intermediate formation of a liquid in the layer
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2207/00—Compositions specially applicable for the manufacture of vitreous enamels
- C03C2207/02—Compositions specially applicable for the manufacture of vitreous enamels containing ingredients for securing a good bond between the vitrified enamel and the metal
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- 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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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
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- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
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- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
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- C04B2235/3213—Strontium oxides or oxide-forming salts thereof
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- 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
- C04B2235/3284—Zinc oxides, zincates, cadmium oxides, cadmiates, mercury oxides, mercurates or oxide forming salts thereof
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/80—Phases present in the sintered or melt-cast ceramic products other than the main phase
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
- C04B2235/9607—Thermal properties, e.g. thermal expansion coefficient
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- Chemical Kinetics & Catalysis (AREA)
- Ceramic Engineering (AREA)
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Abstract
本发明涉及高度结晶的玻璃料烧结的玻璃陶瓷材料,以及使用它们制备的密封物,该密封物适用于固体氧化物燃料电池应用。该密封物的热膨胀系数在70-130×10-7/℃的范围内,优选为85-115×10-7/℃。该玻璃陶瓷材料包含晶体组分和玻璃组分,在玻璃陶瓷中的晶体组分>50%,而玻璃组分<50%。在一个优选的实施方式中,晶体组分>75%。仅关于晶体组分,玻璃陶瓷的晶体组分中>50重量%的晶体具有选自以下物质表示的结构:瓦硅钙钡石、假硅灰石、μ-(Ca,Sr)SiO3、六方钾霞石、钾霞石和硅灰石(主晶相),晶体组分中剩余的<50%是至少一个次晶相。通常,本发明的玻璃陶瓷材料可用作金属-金属、金属-陶瓷和陶瓷-陶瓷的密封剂。
Description
相关申请
本申请涉及并要求于2006年4月11日提交的同时待审的题为“高热膨胀环硅酸盐玻璃陶瓷(HIGH THERMAL EXPANSION CYCLOSILICATEGLASS-CERAMICS)”的美国专利申请第11/402,761号的优先权。该同时待审的申请第11/402,761号和本申请具有共同的发明人Linda R.Pinckney,共同转让给康宁股份有限公司(Corning Incorporated),以及同时待审的还有于2006年10月11日提交的题为“用于固体氧化物燃料电池的玻璃陶瓷密封物(Glass Ceramic Seals For Use In Solid Oxide Fuel Cells)”的美国专利申请第11/546,237号。
发明领域
本发明涉及高度结晶的玻璃料烧结的玻璃陶瓷,其中主晶相具有文中所述的选择的晶体结构,更具体涉及使用本发明所述的玻璃陶瓷材料作为密封剂制成的固体氧化物燃料电池(“SOFC”)的密封物。除了SOFC用途外,该材料可用作金属-金属、金属-陶瓷和陶瓷-陶瓷密封的密封剂。
发明背景
玻璃陶瓷是由前体玻璃制品的受控结晶形成的多晶材料。玻璃陶瓷可通过对玻璃整料进行热处理使其转化为晶态而制得。这称为“整体(bulk)”或“整料(monolith)玻璃陶瓷成形法”。Stookey的美国专利第2,900,971号描述了整料玻璃陶瓷成形技术。通常,使通常含有成核剂的原料熔融,同时冷却形成所需几何形状的玻璃整料。然后,对玻璃整料进行结晶热处理,该处理在本领域中称为“陶瓷化(ceramming)”。合适的热处理通常包括低温保持在转变区域附近,以诱导成核,然后一个或多个温度保持在玻璃软化点以上,以促进晶体生长。在整料成形法中,成核在内部发生。通过整体成形法制备玻璃陶瓷适合于玻璃制品成形和制造中使用的高速自动制造方法。另外,内部成核的一个优点是可以提供各种各样的多晶微结构。因此,通过调节温度处理范围,可以改变最终玻璃陶瓷材料的性质。
玻璃陶瓷还可以在称为粉末处理法的方法中通过烧制玻璃料制得。使玻璃减小到粉末状态(玻璃料),成形为所需的形状,然后烧制和结晶为玻璃陶瓷状态。在此过程中,玻璃颗粒的表面用作晶相的成核位点。对玻璃组成、粒度和处理条件进行选择,使得玻璃在结晶之前软化,并且刚好在结晶过程完成之前粘性烧结到最大密度。成形方法可包括但不限于挤出、滑移浇铸、带浇铸、喷雾干燥和等静压压制。
玻璃陶瓷材料具有使它们适用于许多其它应用的性质。玻璃陶瓷材料最近日益重要的应用是作为固体氧化物燃料电池(“SOFC”)的密封剂。SOFC基本上是化学能转化为电能的能量反应系统。虽然它们与蓄电池类似,但是不同之处在于它们不像蓄电池一样会耗尽,因为对SOFC连续地供给燃料,因此能够连续地提供电力。因此,它们只受燃料有效供给的限制,就像任何正规的发电厂一样。SOFC在600-1000℃的高温下工作,但是目前的研究试图降低此温度范围,以及将陶瓷材料用于电池的功能元件。
作为一般的描述,SOFC由阳极和阴极以及将它们隔开的固体不可渗透的电解质组成,所述电解质将氧离子从阴极传导到阳极,在阳极氧离子与燃料发生化学反应。离子通过电解质所诱导的电荷被集中起来,从电池传导到使用源。虽然每个电池仅产生有限的电压,但是可以将多个电池串联起来将电压增加到可用功率的水平。在全世界,5-10千瓦的小型SOFC装置可从各种公司购得,25-125千瓦的大型装置仍然在开发或测试中。
当设计SOFC时,重要的是将燃料(H2、CH4、C2H8、CO等)和空气(O2)流保持分开,保持热平衡,使得装置的工作温度保持在可接受的范围内。为了确保这两点得以实现,陶瓷材料广泛用于SOFC的设计中。但是,为了制造产生可用量的功率的装置需要多个单电池串联,因此不仅需要工作部件与单个电池保持分开(无泄漏),而且需要串联电池中电池与电池之间无泄漏。虽然已经有各种材料用作密封剂,例如环氧化物和水泥等,但是该领域还需要改进。本发明揭示了可用作密封材料的玻璃陶瓷材料。
本发明涉及用于固体氧化物燃料电池的密封物,以及适用于形成供此用途之用的玻璃陶瓷密封剂的新组合物。
发明概述
本发明的一方面涉及用于固体氧化物燃料电池的无硼玻璃陶瓷密封物,所述密封物包括包含<50%玻璃组分和>50%晶体组分的玻璃陶瓷。仅关于晶体组分,玻璃陶瓷的晶体组分中>50重量%的晶体具有选自以下物质表示的结构:瓦硅钙钡石(walstromite)、假硅灰石(cyclowollastonite)和μ-(Ca,Sr)SiO3(环硅酸盐材料)和它们的混合物(主晶相)。除了上述晶相外,玻璃陶瓷的陶瓷部分中还可以存在一种或多种其它晶相(<50%),这类晶相组成玻璃陶瓷的陶瓷(晶体)部分的其余部分(次晶相)。这类其它晶相的例子包括但不限于具有以下物质表示的结构的晶体:硅灰石、透辉石、顽辉石、镁橄榄石或它们的混合物。这些玻璃陶瓷的CTE(25°-800℃)在70-130 x 10-7/℃的范围内,优选为85-115 x 10-7/℃。
本发明的一方面涉及可用于固体氧化物燃料电池的高度结晶的无硼玻璃陶瓷密封物,所述密封物含有>75%的晶体组分和<25%或更低的玻璃组分。在一个优选的实施方式中,晶体组分>90%,玻璃组分<10%。这些玻璃陶瓷的CTE在70-130 x 10-7/℃的范围内,优选为85-115 x 10-7/℃。
本发明的另一方面涉及无硼玻璃陶瓷密封物,其中玻璃陶瓷含有SiO2、Al2O3和至少一种MO组分,MO是Mg、Ca、Ba和Sr的碱土氧化物,玻璃陶瓷的晶体组分中>50%的晶体具有选自以下物质表示的结构:瓦硅钙钡石、假硅灰石和μ-(Ca,Sr)SiO3以及它们的混合物。另外,上述玻璃陶瓷密封物可任选地含有少量其它氧化物如ZnO、Nb2O5、Ta2O5、La2O3、Y2O3、Sb2O3和过渡金属和稀土氧化物。此外,玻璃陶瓷的陶瓷部分中还可以存在一种或多种其它晶相,这类晶相组成玻璃陶瓷的陶瓷部分的其余部分。这类其它晶相的例子包括但不限于具有以下物质表示的结构的晶体:硅灰石、透辉石、顽辉石、镁橄榄石,和它们的固溶体组合物或混合物。这些玻璃陶瓷的CTE在85-115 x 10-7/℃的范围内。
本发明的另一方面涉及一种无硼玻璃陶瓷密封物,其组成包括30-50重量% SiO2,2-8重量% Al2O3,10-40重量%CaO,以及0-40重量% SrO、0-35重量% BaO、0-10重量% MgO中的至少一种,其中碱土氧化物的总含量(∑MO,其中M是Mg、Ca、Ba和Sr中的两种或多种)为40-60重量%。任选地,在该组合物中还可以任选地包含最多8重量%的ZnO和最多10重量%的Nb2O5、Ta2O5、La2O3、Y2O3或Sb2O3(或它们的混合物)。这些玻璃陶瓷的CTE在85-115 x 10-7/℃的范围内。按照范围区间表示,当该组合物中包含任选的氧化物时,这些氧化物所选择的量对于ZnO而言在>0-8重量%的范围内,而对于Nb2O5、Ta2O3、La2O3、Y2O3、Sb2O5而言在>0-10%的范围内。
本发明的另一方面涉及包含>50%晶体组分和<50%玻璃组分的无硼、无锌玻璃陶瓷密封物;仅关于晶体组分,玻璃陶瓷中>50重量%的晶体组分是选自下组的晶相:铝硅酸钾六方钾霞石(kalsilite)和钾霞石(kaliophilite),以及硅灰石(主晶相)。除了上述晶相外,还可以包含一种或多种其它晶相如钙铝黄长石、钙长石、斜方硅钙石和刚玉,这类晶相组成玻璃陶瓷的晶体组分的其余部分(次晶相)。这些玻璃陶瓷的CTE在70-130 x 10-7/℃的范围内,优选为85-115 x 10-7/℃。在一个实施方式中,无硼、无锌玻璃陶瓷密封物的组成为5-25重量%的Al2O3、25-45重量%的CaO、25-45重量%的SiO2、1-10重量%的K2O和0-25重量%的GeO2。在另一个实施方式中,无硼、无锌玻璃陶瓷密封物的组成为10-20重量%的Al2O3、30-40重量%的CaO、30-40重量%的SiO2、2-8重量%的K2O和5-20重量%的GeO2。
在选择的实施方式(a)无硼、无锌玻璃陶瓷,(b)无硼玻璃陶瓷和(c)含有SiO2、Al2O3和至少一种MO组分的无硼玻璃陶瓷中,晶体组分的主晶相>75%,一个或多个次晶相(如果存在)小于晶体组分的25%。在另一个实施方式中,主晶相>90%,一个或多个次晶相(如果存在)小于晶体组分的10%
发明详述
文中所用的所有组成以整体重量百分数(重量%)表示,包括指定的晶体组分或相和玻璃组分的百分数。为了清楚起见,在本领域中术语“玻璃陶瓷”应理解为指含有玻璃相或组分和均匀地分散在整个玻璃中的晶体相或组分的材料。应理解,本发明的组合物可含有痕量元素,在此指<0.4重量%,优选<0.1重量%。
如同本发明中应理解且举例的,“玻璃陶瓷的晶体组分中>50%的晶体具有选自由瓦硅钙钡石、假硅灰石和μ-(Ca,Sr)SiO3表示的结构”是涉及由“名称”瓦硅钙钡石、假硅灰石和μ-(Ca,Sr)SiO3表示的结构,而不涉及它们所表示的晶体材料的分子式。例如,瓦硅钙钡石和假硅灰石典型(端员(endnumber))的分子式分别是Ca2BaSi3O9和α-CaSiO3。本发明所述的密封材料可含有固溶体结构的其它元素(参见表1的实施例1-7),但是晶相中>50%的晶体将具有瓦硅钙钡石和假硅灰石结构,并可包含这类其它元素。晶体组分中晶体的其余部分(即<50%)将构成次晶相,如果该相存在的话。文中所提及的各种结构的典型(端员)分子式是:瓦硅钙钡石[Ca2BaSi3O9],假硅灰石[α-CaSiO3],硅灰石(β-CaSiO3),透辉石(CaMgSi2O6),镁黄长石(Ca2MgSi2O7),锌黄长石(Ca2MgSi2O7),顽辉石(MgSiO3),镁橄榄石(Mg2SiO4),钙铝黄长石[Ca2Al2SiO7],钙长石[Ca2Al2Si2O8],斜方硅钙石[Ca6(SiO4)(Si3O10)]和刚玉[Al2O3]。
本发明涉及用于固体氧化物燃料电池的无硼玻璃陶瓷密封物,所述密封物包括包含玻璃组分和晶体组分的玻璃陶瓷。在一个实施方式中,玻璃陶瓷的晶体组分>50重量%,玻璃组分<50%。在另一个实施方式中,玻璃陶瓷的晶体组分>75重量%,玻璃组分<25重量%。在另一个实施方式中,玻璃陶瓷的晶体组分>90%,玻璃组分<10%。在另一个实施方式中,本发明涉及用于固体氧化物燃料电池的无硼、无锌玻璃陶瓷密封物,所述密封物包括包含玻璃组分和晶体组分的玻璃陶瓷,各组分(玻璃或陶瓷)的百分含量如同该段落中无硼玻璃陶瓷密封物的实施方式中给出的百分含量。
仅关于玻璃陶瓷的晶体组分,≥50重量%的晶体组分(在下文中称为主晶相)具有选自以下的结构:瓦硅钙钡石、假硅灰石和μ-(Ca,Sr)SiO3、上述晶体结构的固溶体和混合物,或者铝硅酸钾六方钾霞石和钾霞石[KAlSiO4]的结构,以及硅灰石,和它们的混合物。除了上述主晶相外,玻璃陶瓷的晶体组分中还可以存在一种或多种其它晶相或次晶相(该其余部分小于晶体组分的50%),这类晶相组成玻璃陶瓷的晶体组分的其余部分。这类次晶相的例子可包括但不限于镁黄长石、锌黄长石、硅灰石、透辉石、顽辉石和镁橄榄石。例如,如果晶体组分中主晶相是75%的假硅灰石,则其余部分即次晶相可以是25%的镁黄长石(如果存在镁)或锌黄长石(如果存在锌)。本领域技术人员将理解次晶相的确切种类和量将取决于玻璃的组成。
密封物是固体氧化物燃料电池(SOFC)平面设计的整体部分;它们防止燃料和空气相混,并且保持燃料不从电池堆或单个电池中泄漏。对密封物的要求是非常严格的,因而对形成密封物的密封剂或密封材料的要求也非常严格。例如,密封物必须能够承受置于高达1000℃的高温下,以及置于氧化和还原环境中。另外,密封物必须具有低蒸气压,必须在电池堆的使用寿命(可能超过50,000小时)内保持密封和绝缘。此外,密封物必须不会由于电池堆的热循环或由于粘度和化学组成随时间变化而劣化。这些变化可能是由于某些物质的挥发性以及与其它燃料电池部件如电极和不锈钢互连的反应造成的。最后,密封物本身必须不是污染源,否则将对其它电池堆部件,特别是电池电极的工作有不利的影响。
最常用的密封剂是水泥、玻璃和玻璃陶瓷。水泥密封通常不形成无泄漏的密封,而玻璃密封可以提供所需的气密性,它们可以使用的上限温度通常是有限的。玻璃陶瓷用作密封剂即使不能完全也可以最大程度地避免这些问题。
粉末处理的(玻璃料烧结的)玻璃陶瓷是众所周知的用作金属-金属、金属-陶瓷和陶瓷-陶瓷密封材料以及用于金属和陶瓷的高性能涂料的材料。与玻璃相比,玻璃陶瓷提供更高的使用温度,更优越的机械性能和耐腐蚀性,以及非常宽范围的热膨胀系数(CTE),这使得它们可以用作许多不同合金的膨胀匹配的密封物。在形成玻璃陶瓷的结晶过程中由于熔融玻璃的粘性流动而填充凹角和复杂内部形状的能力使得玻璃陶瓷材料特别适用于系统的高强度非常重要的应用。
然而,甚至许多玻璃陶瓷密封物,特别是含有明显玻璃组分和/或容易扩散的阳离子如小碱离子的那些玻璃陶瓷密封物,可能太易于与SOFC部件反应,随后可发生器件随时间而劣化。在一个实施方式中,本发明涉及高度结晶的玻璃陶瓷密封物,其含有小于25%的残余玻璃(晶体组分与玻璃组分的比例>75/<25),特别适合用于SOFC应用。在另一个实施方式中,本发明涉及高度结晶的玻璃陶瓷密封物,其含有小于20%的残余玻璃(晶体组分与玻璃组分的比例>80/<20),特别适合用于SOFC应用。在又一个实施方式中,本发明涉及高度结晶的玻璃陶瓷密封物,其含有小于10%的残余玻璃(晶体组分与玻璃组分的比例>90/<10)。全部玻璃陶瓷密封物具有与燃料电池电解质和互连精密匹配的热膨胀,最终微结构中残余的玻璃组分被限制在空隙和一些晶粒间界中,不形成通过密封物的连续通道。
本发明的高度结晶的玻璃陶瓷密封材料的优点包括:
·它们通过瞬时玻璃相有利的烧结性提供低应力气密密封的途径。
·接近零的孔隙率和不连续玻璃相:任何残余的玻璃占据空隙,不形成通过材料的主体的连续通道。这样将高温下阳离子通过玻璃相的迁移减至最小,因而抑制了基材和玻璃料之间任何连续的反应。
·最少的残余玻璃还能避免玻璃陶瓷密封物在热循环过程中发生软化或永久的尺寸变化。
·密封物具有机械和热稳定性。
·结晶的密封物的热膨胀与SOFC部件的热膨胀匹配。
对于高度结晶的玻璃陶瓷SOFC密封物的要求是它们具有接近化学计量比的组成,使得它们能够经历几乎完全的结晶,因而提供SOFC应用所需的高热膨胀。符合这些标准的玻璃陶瓷包括其中晶相的晶体具有某种结构的玻璃陶瓷,所述结构选自以下物质表示的结构:瓦硅钙钡石、假硅灰石和μ-(Ca,Sr)SiO3结构,并且次相结构是基于包括但不限于以下的结构:硅灰石、透辉石、镁黄长石、锌黄长石、顽辉石和镁橄榄石。
在本发明的另一方面,玻璃陶瓷中>50重量%的晶体组分选自铝硅酸钾六方钾霞石和钾霞石,次相包括但不限于硅灰石、钙黄长石、钙长石、斜方硅钙石和刚玉。这些玻璃陶瓷的CTE在70-130 x 10-7/℃的范围内,优选为85-115 x 10-7/℃。
下表1和2例举了一些可用作SOFC应用的密封物的组成(重量%)。由表1所例举的玻璃陶瓷材料制成的密封物含有SiO2、Al2O3和MO,其中MO是Mg、Ca、Ba和Sr的碱土氧化物。表1所例举的玻璃陶瓷的主(>50%)晶相是瓦硅钙钡石、假硅灰石和μ-(Ca,Sr)SiO3中的至少一种,次(<50%)相是硅灰石、透辉石、镁黄长石、顽辉石、镁橄榄石和锌黄长石、以及它们的固溶体或混合物。
表1所例举的可用作SOCF密封物的玻璃陶瓷材料的组合物是含有SiO2、Al2O3和MO的玻璃陶瓷,其中MO是Mg、Ca、Ba和Sr的碱土氧化物,碱土氧化物的含量之和(∑MO,其中M是Mg、Ca、Ba和Sr中的两种或多种)是40-60重量%;Al2O3为2-4重量%;SiO2为36-58重量%。
由表2所例举的玻璃陶瓷材料制成的无硼、无锌密封物含有SiO2、Al2O3、CaO和R2O,其中R是碱离子,优选是钾(K)。表2所例举的玻璃陶瓷的晶体组分具有其结构选自钾霞石和六方钾霞石结构的主晶相,还可具有包括但不限于硅灰石、钙铝黄长石和刚玉的次晶相。表2的无硼、无锌玻璃陶瓷密封物的组成为5-25重量%的Al2O3、25-45重量%的CaO、25-45重量%的SiO2、1-10重量%的K2O和0-25重量%的GeO2。在优选的实施方式中,无硼、无锌玻璃陶瓷密封物的组成为10-20重量%的Al2O3、30-40重量%的CaO、30-40重量%的SiO2、2-8重量%的K2O和5-20重量%的GeO2。
表1
表(1)续
表2
样品号 | (11) | (12) | (13) |
Al 2 O 3 | 15.3 | 15.3 | 15.3 |
CaO | 33.6 | 33.6 | 33.5 |
SiO 2 | 36 | 35.9 | 35.9 |
K 2 O | 4.9 | 4.2 | 3.5 |
GeO 2 | 10.2 | 11 | 11.8 |
可用于制备本发明的玻璃陶瓷的玻璃组合物通过以下方法制得:在1450-1650℃的温度下,将组分材料在铂坩锅之类的容器中熔融2-5小时。原料可以是本领域中已知的可用于制备玻璃的文中所述金属的氧化物、碳酸盐、硝酸盐、氢氧化物和forma。在一些实施方式中,熔融可以在1600±50℃的温度下进行2.5-4小时。对于各组合物,由熔融的玻璃组合物形成较小的大约5厘米的片,在750±40℃的温度下退火。这些样品用作整体玻璃稳定性的目测指示。将各坩锅中剩余的玻璃加入水中,研磨至平均粒度为10-20微米(325目)。使用本领域已知的技术将所得玻璃料(玻璃料=粉状玻璃)粉末成形为制品(小球、棒、杆等)。例如,对于本文所述的测试来说,将玻璃料干压成12.76厘米直径(0.5英寸)的小球和/或10 x0.6 x 0.6厘米的CTE棒(4 x 0.25 x 0.25英寸),然后在850℃-1000℃的温度下烧制(烧结)1-2小时。
本发明的玻璃陶瓷组合物的热膨胀系数在70-130 x 10-7/℃的范围内,优选为85-115 x 10-7/℃。为了用作SOFC密封物,在一个优选的实施方式中,高度结晶的玻璃陶瓷密封物的晶相>75重量%,玻璃相<25重量%。在另一个优选的实施方式中,晶相>90重量%,玻璃相<10重量%。
本发明所提及的晶体形式的相和结构信息可以从陶瓷制造者用的相图(Phase Diagrams for Ceramists)和本领域技术人员已知的其它来源获得;例如,XRD信息可参见JCPDS数据库,用于鉴别玻璃陶瓷中存在的晶体形式。
虽然已经关于有限数目的实施方式描述了本发明,但是受益于本说明书的本领域技术人员将会理解在不背离本文所揭示的本发明范围的情况下可以作出其它实施方式。因此,本发明的范围应该仅由所附权利要求书限定。
Claims (19)
1.一种用于固体氧化物燃料电池的玻璃陶瓷密封物,所述密封物包括包含玻璃组分和晶体组分的玻璃陶瓷,
其中:
所述玻璃陶瓷是无硼的;
所述玻璃陶瓷的晶体组分>50%,而玻璃陶瓷密封物中的玻璃组分<50%;
仅就晶体组分而言,>50重量%的晶体组分构成主晶相,该主晶相中的晶体的结构选自以下物质表示的结构:瓦硅钙钡石、假硅灰石和μ-(Ca,Sr)SiO3、六方钾霞石、钾霞石和硅灰石,
剩余的<50%的晶体组分构成至少一个次晶相;和
所述玻璃陶瓷的CTE在70-130 x 10-7/℃的范围内。
2.如权利要求1所述的玻璃陶瓷密封物,其特征在于,所述玻璃陶瓷物包含SiO2、Al2O3;选自钙、钡、镁和锶氧化物中的至少一种氧化物;
任选地,所述玻璃陶瓷含有选自下组的至少一种氧化物:ZnO、Nb2O5、Ta2O3、La2O3、Y2O3、Sb2O5和过渡金属氧化物。
3.如权利要求1所述的玻璃陶瓷密封物,其特征在于,所述玻璃陶瓷的晶体组分>75重量%,而玻璃组分<25%;主晶相大于晶体组分的75%。
4.如权利要求1所述的玻璃陶瓷密封物,其特征在于,所述玻璃陶瓷的晶体组分>90重量%,而玻璃组分<10%。
5.如权利要求1所述的玻璃陶瓷,其特征在于,所述玻璃陶瓷的CTE在85-115 x 10-7/℃的范围内。
6.一种用于固体氧化物燃料电池的玻璃陶瓷密封物,所述密封物包括包含>75重量%的晶体组分和<25重量%的玻璃组分的无硼玻璃陶瓷玻璃料材料,
其中:
晶体组分含有>50%的主晶相,主晶相的结构选自瓦硅钙钡石、假硅灰石和μ-(Ca,Sr)SiO3的结构,
剩余的<50%的晶体组分构成至少一个次晶相;和
所述玻璃陶瓷密封物的CTE在70-130 x 10-7/℃的范围内。
7.如权利要求6所述的玻璃陶瓷密封物,其特征在于,所述玻璃料材料包含SiO2、Al2O3和MO,其中MO是Mg、Ca、Ba和Sr的碱土氧化物;
所述玻璃料材料的CTE在85-115 x 10-7/℃的范围内;
任选地,所述玻璃陶瓷含有选自下组的至少一种氧化物:ZnO、Nb2O5、Ta2O3、La2O3、Y2O3、Sb2O5和过渡金属氧化物。
8.如权利要求7所述的玻璃陶瓷密封物,其特征在于,ΣMO在40-60重量%的范围内,其中M是Mg、Ca、Ba和Sr中的两种或多种,Al2O3为2-8重量%,剩余为SiO2;
当所述组合物中包含所述任选的氧化物时,这些氧化物所选择的量对于ZnO和过渡金属氧化物而言在>0-8重量%的范围内,而对于Nb2O5、Ta2O3、La2O3、Y2O3、Sb2O5而言在>0-10%的范围内。
9.如权利要求8所述的玻璃陶瓷,其特征在于,所述任选的组分是>0-6重量%的氧化锌。
10.如权利要求6所述的玻璃陶瓷,其特征在于,所述次晶相具有选自下组结构的结构:硅灰石、透辉石、顽辉石、镁橄榄石和它们的固溶体或混合物。
11.如权利要求10所述的玻璃陶瓷,其特征在于,所述主晶相大于晶体组分的75%。
12.如权利要求10所述的玻璃陶瓷,其特征在于,所述主晶相大于晶体组分的90%。
13.一种用于固体氧化物燃料电池的玻璃陶瓷密封物,所述密封是包含以下组分的无硼玻璃陶瓷玻璃料材料:
30-50重量%SiO2,2-8重量%Al2O3,10-40重量%CaO,和0-40重量%SrO、0-35重量%BaO、0-10重量%MgO中的至少一种;和
任选地,至少一种选自下组的氧化物:ZnO、Nb2O5、Ta2O3、La2O3、Y2O3、Sb2O5和过渡金属氧化物,
其中ΣMO在40-60重量%的范围内,其中M是Mg、Ca、Ba和Sr中的一种或多种,
当所述组合物中包含所述任选的氧化物时,这些氧化物所选择的量对于ZnO和过渡金属氧化物而言在>0-8重量%的范围内,而对于Nb2O5、Ta2O3、La2O3、Y2O3、Sb2O5而言在>0-10%的范围内。
14.如权利要求13所述的玻璃陶瓷密封物,其特征在于,所述密封物包含>75%的晶体组分和<25%的玻璃组分,
所述晶体组分含有>50%的主晶相,主晶相的结构选自瓦硅钙钡石、假硅灰石和μ-(Ca,Sr)SiO3的结构,包括上述晶相中至少两种的固溶体和混合物,晶体组分中剩余部分是<50%的一种或多种次晶相。
15.如权利要求14所述的玻璃陶瓷密封物,其特征在于,晶相>90%,玻璃相<10%。
16.如权利要求14所述的玻璃陶瓷密封物,其特征在于,所述密封物的CTE在85-115 x 10-7/℃的范围内。
17.一种用于固体氧化物燃料电池的玻璃陶瓷密封物,所述密封物包括包含<50%玻璃组分和>50%晶体组分的无硼、无锌玻璃陶瓷,
其中:
仅就晶体组分而言,>50重量%的晶体组分构成>50%的主晶相,该主晶相中的晶体的结构选自以下物质表示的结构:六方钾霞石、钾霞石和硅灰石,以及它们的固溶体或混合物;
剩余的<50%的晶体组分构成次晶相,所述次晶相选自以下物质表示的结构:镁黄长石、锌黄长石、刚玉、钙黄长石、钙长石、硅灰石、透辉石、顽辉石和镁橄榄石、它们的混合物;
所述玻璃陶瓷密封物的CTE在70-130 x 10-7/℃的范围内;和
所述密封物包含5-25重量%的Al2O3、25-45重量%的CaO、25-45重量%的SiO2、1-10重量%的K2O和0-25重量%的GeO2。
18.如权利要求18所述的无硼、无锌玻璃陶瓷密封物,其特征在于,所述密封物包含10-20重量%的Al2O3、30-40重量%的CaO、30-40重量%的SiO2、2-8重量%的K2O和5-20重量%的GeO2。
19.如权利要求18所述的玻璃陶瓷密封物,其特征在于,所述密封物的CTE在85-115 x 10-7/℃的范围内。
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DE10346197B4 (de) * | 2003-09-30 | 2006-02-16 | Schott Ag | Glaskeramik, Verfahren zur Herstellung einer solchen und Verwendung |
US7214441B2 (en) * | 2005-02-03 | 2007-05-08 | Corning Incorporated | Low alkali sealing frits, and seals and devices utilizing such frits |
-
2006
- 2006-04-11 US US11/402,761 patent/US7378361B2/en active Active
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2007
- 2007-04-05 CN CN2007800128770A patent/CN101421199B/zh not_active Expired - Fee Related
- 2007-04-05 CN CN2007800175004A patent/CN101506117B/zh not_active Expired - Fee Related
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Also Published As
Publication number | Publication date |
---|---|
CN101421199B (zh) | 2012-04-04 |
US7378361B2 (en) | 2008-05-27 |
US20070238599A1 (en) | 2007-10-11 |
CN101506117B (zh) | 2013-01-02 |
CN101421199A (zh) | 2009-04-29 |
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