CN103288349B - A kind of sealing glass ceramic and preparation and application thereof - Google Patents
A kind of sealing glass ceramic and preparation and application thereof Download PDFInfo
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- CN103288349B CN103288349B CN201310200396.XA CN201310200396A CN103288349B CN 103288349 B CN103288349 B CN 103288349B CN 201310200396 A CN201310200396 A CN 201310200396A CN 103288349 B CN103288349 B CN 103288349B
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Abstract
The invention discloses a kind of sealing glass ceramic and preparation and application thereof, raw material consists of B
2o
3, Al
2o
3, SiO
2, the mixture of one or more in MO(MgO, CaO, SrO, BaO) and NiO, its mol ratio is 0 ~ 10:0 ~ 5:25 ~ 60:20 ~ 50:5 ~ 30.Promote the formation of devitrified glass owing to adding NiO, effectively reduce and to the diffusion of seal glass, significantly improve the stability at elevated temperature of sealing glass ceramic containing Cr ion in the connection extremely of Cr Stainless Steel Alloy; In addition, NiO significantly reduces the package temperature of glass, avoids excessive temperature to the destruction of other elements.Raw materials of the present invention is simple, and be easy to get, process stabilizing, obtains with SiO
2for the inverse glass network structure of main body, cost is low, and technique is simple, feasible, reaches practical and industrialized condition.
Description
Technical field
The invention belongs to field of solid oxide fuel, be specifically related to a kind of there is stability at elevated temperature sealing glass ceramic and preparation and use.
Background technology
The advantages such as Solid Oxide Fuel Cell (SOFC) adopts soild oxide (pottery) ionogen, and at high temperature run, have generating efficiency high, the cost of material is low, the compatible various fuel of energy (as methane, coal gas, methyl alcohol, alcohol, oil liquefied gas etc.).But the subject matter that exploitation SOFC faces is that at high temperature how fuel gas and oxic gas effectively completely cut off and sealing-in.Due to the working temperature of battery high (700 ~ 750 ° of C), suitable seal, sealing materials and sealing technology is selected to become the key of restriction planar SOFC development.For solving seal, sealing materials and containing the stainless sealing-in Problem of Failure of Cr, domestic and international investigator have employed: 1. carry out preoxidation to containing Cr alloy linker, to reduce seal, sealing materials and the surface reaction containing Cr alloy; 2. to armor coated containing Cr alloy linker, to limit the diffusion of Cr; 3. by improving the uniform recipe design surface reaction of devitrified glass, the Loehman as Sandia National Laboratory of the U.S. also attempts the Cr adding saturation concentration to glass basis
2o
3to suppress the diffusion of Cr; 4. utilize alkalimetal oxide (as Na
2o and K
2o) replace the methods such as the alkaline earth metal oxide that easily reacts, but above method all fails to satisfactorily resolve the sealing-in Problem of Failure that surface reaction causes.
For seal, sealing materials and other interelements because coefficient of thermal expansion mismatch is (as seal glass 11 ~ 13 × 10
-6/ K, chromium stainless steel alloy linker ~ 13 × 10
-6/ K) cause the generation of thermal stresses, and then bring out the initiation and propogation of crackle, so that the defect of sealing-in ultimate failure, domestic and international research drops into great effort exploitation at high temperature can the self-healing seal, sealing materials of long term maintenance vitreous state, attempts the thermal stresses of the viscous flow release seal interface accumulation by glassy phase.But, easily react under SOFC working temperature with containing Cr alloy linker for the network ligand ion (as IIA race) improving seal glass viscosity, generate as BaCrO
4, SrCrO
4and CaCrO
4etc. having high thermal expansivity (18 ~ 20 × 10
-6/ K) product, again cause the coefficient of thermal expansion mismatch with other elements of seal interface, destroy sealing-in bonding force, the work-ing life of serious restriction seal, sealing materials and SOFC, especially in the stability of Thermal Cycling.
Summary of the invention
In order to solve the problem, the invention provides a kind of sealing glass ceramic and preparation and application thereof, by adding the NiO of proper content, promote the formation of devitrified glass, the stability at elevated temperature of material can be made to improve further.
The present invention implements by following technical solution:
A kind of raw material of sealing glass ceramic consists of B
2o
3, Al
2o
3, SiO
2, the mixture of one or more in MO(MgO, CaO, SrO, BaO) and NiO, its mol ratio is 0 ~ 10:0 ~ 5:25 ~ 60:20 ~ 50:5 ~ 30.
The method preparing sealing glass ceramic as above comprises the following steps:
(1) raw material is mixed; Found through 1300-1400 DEG C, soaking time 1-4 hour; To the glass metal melted, carry out chilling, obtain glass frit; Then, pulverized by glass frit, grinding or ball milling, obtain glass powder after sieving;
(2) by glass powder and binding agent, dispersion agent and solvent form slurry, in ball mill, ball milling is dispersed; Flow casting molding, seasoning, is then cut into the idiosome of desired shape, makes glass sealing material.
The binding agent of described step (2) is epoxy resin, methylcellulose gum, polyvinyl butyral acetal, the mixture of one or more in polyvinyl alcohol.
The dispersion agent of described step (2) is the mixture of one or more in fish oil, polyacrylic acid, polyvinyl alcohol, polyacrylamide.
The solvent of described step (2) is the mixture of one or more in water, ethanol, Virahol, propyl carbinol, toluene, dimethylbenzene, acetone.
Glass sealing material is placed in and treats sealing-in position, with the ramp of 1-5 DEG C/min in electric furnace, 400-500 DEG C insulation 0.5-2 hour, then with the ramp of 1-5 DEG C/min to 750-850 DEG C of Crystallizing treatment 0.5-2 hour, namely complete sealing-in.
Remarkable advantage of the present invention is:
(1) the present invention promotes the formation of devitrified glass owing to adding NiO, effectively reduces and to the diffusion of seal, sealing materials, significantly improves the stability at elevated temperature of sealing glass ceramic containing Cr ion in the connection extremely of Cr Stainless Steel Alloy;
(2) NiO also significantly reduces the package temperature of glass, avoids excessive temperature to the destruction of other elements;
(3) raw materials of the present invention's selection is simple, is easy to get, process stabilizing.Select corresponding oxide compound to be source material, make their Homogeneous phase mixing, remain a high proportion of mixing and distribution state in fusing and subsequent heat treatment, obtain with SiO
2for the inverse glass network structure of main body, cost is low, and technique is simple, feasible, reaches practical and industrialized condition.
Accompanying drawing explanation
Fig. 1 is traditional borosilicate microcrystalline glass in series (not containing NiO) and Cr
2o
3the ultraviolet spectrogram of powder solid state reaction product at 800 DEG C.
Fig. 2 is the ultraviolet spectrogram of devitrified glass under parallel laboratory test condition of interpolation 5% NiO.
Fig. 3 is the ultraviolet spectrogram of devitrified glass under parallel laboratory test condition of interpolation 10% NiO.
Fig. 4 is the ultraviolet spectrogram of devitrified glass under parallel laboratory test condition of interpolation 18% NiO.
Fig. 5 is the ultraviolet spectrogram of devitrified glass under parallel laboratory test condition of interpolation 25% NiO.
Fig. 6 is the ultraviolet spectrogram of devitrified glass under parallel laboratory test condition of interpolation 30% NiO.
Fig. 7 is the thermal dilatometry of the devitrified glass adding different content NiO.
Embodiment
A kind of raw material of sealing glass ceramic consists of B
2o
3, Al
2o
3, SiO
2, the mixture of one or more in MO(MgO, CaO, SrO, BaO) and NiO, its mol ratio is 0 ~ 10:0 ~ 5:25 ~ 60:20 ~ 50:5 ~ 30.
The method preparing sealing glass ceramic as above comprises the following steps:
(1) raw material is mixed; Found through 1300-1400 DEG C, soaking time 1-4 hour; To the glass metal melted, carry out chilling, obtain glass frit; Then, pulverized by glass frit, grinding or ball milling, obtain glass powder after sieving;
(2) by glass powder and binding agent, dispersion agent and solvent form slurry, in ball mill, ball milling is dispersed; Flow casting molding, seasoning, is then cut into the idiosome of desired shape, makes glass sealing material.
The binding agent of described step (2) is epoxy resin, methylcellulose gum, polyvinyl butyral acetal, the mixture of one or more in polyvinyl alcohol.
The dispersion agent of described step (2) is the mixture of one or more in fish oil, polyacrylic acid, polyvinyl alcohol, polyacrylamide.
The solvent of described step (2) is the mixture of one or more in water, ethanol, Virahol, propyl carbinol, toluene, dimethylbenzene, acetone.
Glass sealing material is placed in and treats sealing-in position, with the ramp of 1-5 DEG C/min in electric furnace, 400-500 DEG C insulation 0.5-2 hour, then with the ramp of 1-5 DEG C/min to 750-850 DEG C of Crystallizing treatment 0.5-2 hour, namely complete sealing-in.
Table 1 is the sealing glass ceramic component table (molecular fraction) in embodiment 1-5
Embodiment 1: the preparation of material and sealing-in
According to the proportioning of each component of table 1, take a certain amount of analytical pure raw material (CaO, SrO, SiO
2, Al
2o
3, B
2o
3, NiO), within 24 hours, mix with planetary ball mill ball milling; Then powder is put into platinum crucible, be placed in the air atmosphere of chamber type electric resistance furnace, be heated to 1400 DEG C with 3 DEG C/min, be incubated 1 hour; Then, take out crucible, melt is poured into chilling in deionized water, the dry fragment obtaining glass melt; Grinding, crosses 100 mesh sieves, obtains glass powder.Glass powder and polyvinyl alcohol, fish oil, ethanol and toluene (weight ratio is followed successively by 80%, 2%, 1%, 10%, 7%) are mixed into slurry, and in ball mill, ball milling is dispersed; Flow casting molding, seasoning, is then cut into the idiosome of desired shape; Idiosome is placed in and treats sealing-in position, with the ramp of 2 DEG C/min in electric furnace, 450 DEG C of insulations 1 hour, then with the ramp to 750 of 2 DEG C/min DEG C Crystallizing treatment 2 hours, namely complete sealing-in.Fig. 2 shows, adds devitrified glass and the Cr of 5% NiO
2o
3powder carry out at 800 DEG C the reactivity of solid state reaction after 24 hours be corresponding not containing NiO devitrified glass 85%.Melt after insulation is poured in the stainless steel grinding tool after preheating, obtains the glass cylinder of Φ=10mm, d=25mm, with the test of the heating rate of 10 DEG C/min on NETZSCH DIL 402EP thermal dilatometer, obtain glass transition point and softening temperature.Fig. 7 shows, the glass transition point of adding the seal glass of 5%NiO is 639 DEG C, and softening temperature is 704 DEG C.
Embodiment 2: the preparation of material and sealing-in
According to the proportioning of each component of table 1, take a certain amount of analytical pure raw material (CaO, SrO, SiO
2, Al
2o
3, B
2o
3, NiO), within 24 hours, mix with planetary ball mill ball milling; Then powder is put into platinum crucible, be placed in the air atmosphere of chamber type electric resistance furnace, be heated to 1380 DEG C with 3 DEG C/min, be incubated 1 hour; Then, take out crucible, melt is poured into chilling in deionized water, the dry fragment obtaining glass melt; Grinding, crosses 100 mesh sieves, obtains glass powder.Glass powder and methylcellulose gum, polyvinyl alcohol, propyl carbinol and acetone (weight ratio is followed successively by 82%, 2%, 2%, 8%, 6%) are mixed into slurry, and in ball mill, ball milling is dispersed; Flow casting molding, seasoning, is then cut into the idiosome of desired shape; Idiosome is placed in and treats sealing-in position, with the ramp of 2 DEG C/min in electric furnace, 400 DEG C of insulations 1 hour, then with the ramp to 730 of 2 DEG C/min DEG C Crystallizing treatment 2 hours, namely complete sealing-in.This example is preferably form.Fig. 3 shows, adds devitrified glass and the Cr of 10% NiO
2o
3powder carry out at 800 DEG C the reactivity of solid state reaction after 24 hours be corresponding not containing NiO devitrified glass 70%.Melt after insulation is poured in the stainless steel grinding tool after preheating, obtains the glass cylinder of Φ=10mm, d=25mm, with the test of the heating rate of 10 DEG C/min on NETZSCH DIL 402EP thermal dilatometer, obtain glass transition point and softening temperature.Fig. 7 shows, the glass transition point of adding the seal glass of 10%NiO is 636 DEG C, and softening temperature is 695 DEG C.
Embodiment 3: the preparation of material and sealing-in
According to the proportioning of each component of table 1, take a certain amount of analytical pure raw material (CaO, SrO, SiO
2, Al
2o
3, B
2o
3, NiO), within 24 hours, mix with planetary ball mill ball milling; Then powder is put into platinum crucible, be placed in the air atmosphere of chamber type electric resistance furnace, be heated to 1350 DEG C with 3 DEG C/min, be incubated 1 hour; Then, take out crucible, melt is poured into chilling in deionized water, the dry fragment obtaining glass melt; Grinding, crosses 100 mesh sieves, obtains glass powder.Glass powder and epoxy resin, polyacrylamide, Virahol and toluene (weight ratio is followed successively by 84%, 1.5%, 0.5%, 9%, 5%) are mixed into slurry, and in ball mill, ball milling is dispersed; Flow casting molding, seasoning, is then cut into the idiosome of desired shape; Idiosome is placed in and treats sealing-in position, with the ramp of 2 DEG C/min in electric furnace, 480 DEG C of insulations 1 hour, then with the ramp to 700 of 2 DEG C/min DEG C Crystallizing treatment 2 hours, namely complete sealing-in.This example is preferably form.Fig. 4 shows, adds devitrified glass and the Cr of 18% NiO
2o
3powder carry out at 800 DEG C the reactivity of solid state reaction after 24 hours be corresponding not containing NiO devitrified glass 55%.Melt after insulation is poured in the stainless steel grinding tool after preheating, obtains the glass cylinder of Φ=10mm, d=25mm, with the test of the heating rate of 10 DEG C/min on NETZSCH DIL 402EP thermal dilatometer, obtain glass transition point and softening temperature.Fig. 7 shows, the glass transition point of adding the seal glass of 18%NiO is 624 DEG C, and softening temperature is 688 DEG C.
Embodiment 4: the preparation of material and sealing-in
According to the proportioning of each component of table 1, take a certain amount of analytical pure raw material (CaO, SrO, SiO2, NiO), within 24 hours, mix with planetary ball mill ball milling; Then powder is put into platinum crucible, be placed in the air atmosphere of chamber type electric resistance furnace, be heated to 1300 DEG C with 3 DEG C/min, be incubated 1 hour; Then, take out crucible, melt is poured into chilling in deionized water, the dry fragment obtaining glass melt; Grinding, crosses 100 mesh sieves, obtains glass powder.Glass powder and polyvinyl butyral acetal, polyacrylic acid, Virahol and acetone (weight ratio is followed successively by 83%, 2%, 1%, 9%, 5%) are mixed into slurry, and in ball mill, ball milling is dispersed; Flow casting molding, seasoning, is then cut into the idiosome of desired shape; Idiosome is placed in and treats sealing-in position, with the ramp of 2 DEG C/min in electric furnace, 480 DEG C of insulations 1 hour, then with the ramp to 700 of 2 DEG C/min DEG C Crystallizing treatment 2 hours, namely complete sealing-in.This example is preferably form.Fig. 5 shows, adds devitrified glass and the Cr of 25% NiO
2o
3powder carry out at 800 DEG C the reactivity of solid state reaction after 24 hours be corresponding not containing NiO devitrified glass 42%.Melt after insulation is poured in the stainless steel grinding tool after preheating, obtains the glass cylinder of Φ=10mm, d=25mm, with the test of the heating rate of 10 DEG C/min on NETZSCH DIL 402EP thermal dilatometer, obtain glass transition point and softening temperature.Fig. 7 shows, the glass transition point of adding the seal glass of 25%NiO is 620 DEG C, and softening temperature is 676 DEG C.
Embodiment 5: the preparation of material and sealing-in
According to the proportioning of each component of table 1, take a certain amount of analytical pure raw material (CaO, SrO, SiO
2, Al
2o
3, B
2o
3, NiO), within 24 hours, mix with planetary ball mill ball milling; Then powder is put into platinum crucible, be placed in the air atmosphere of chamber type electric resistance furnace, be heated to 1300 DEG C with 3 DEG C/min, be incubated 1 hour; Then, take out crucible, melt is poured into chilling in deionized water, the dry fragment obtaining glass melt; Grinding, crosses 100 mesh sieves, obtains glass powder.Glass powder and methylcellulose gum, polyacrylic acid, polyvinyl alcohol, Virahol and dimethylbenzene (weight ratio is followed successively by 84%, 1.5%, 1%, 0.5%, 8%, 5%) are mixed into slurry, and in ball mill, ball milling is dispersed; Flow casting molding, seasoning, is then cut into the idiosome of desired shape; Idiosome is placed in and treats sealing-in position, with the ramp of 2 DEG C/min in electric furnace, 480 DEG C of insulations 1 hour, then with the ramp to 700 of 2 DEG C/min DEG C Crystallizing treatment 2 hours, namely complete sealing-in.Fig. 6 shows, adds devitrified glass and the Cr of 30% NiO
2o
3powder carry out at 800 DEG C the reactivity of solid state reaction after 24 hours be corresponding not containing NiO devitrified glass 30%.Melt after insulation is poured in the stainless steel grinding tool after preheating, obtains the glass cylinder of Φ=10mm, d=25mm, with the test of the heating rate of 10 DEG C/min on NETZSCH DIL 402EP thermal dilatometer, obtain glass transition point and softening temperature.Fig. 7 shows, the glass transition point of adding the seal glass of 30%NiO is 615 DEG C, and softening temperature is 671 DEG C.
The present invention obtains the seal glass with sealing-in mobility and stability at elevated temperature by above-mentioned enforcement.Its significant effect embodies a concentrated reflection of the raising aspect of stability at elevated temperature.To seal, sealing materials and Cr
2o
3the product of powder at high temperature solid state reaction is by ultraviolet spectroscopy Cr(VI) absorption intensity, can the chemical stability of quantitative evaluation material, the number of pages being published in " Journal of Power Sources " see this seminar in 2010 6795 to 6797 article.Reactivity is lower, shows that the stability at elevated temperature of seal, sealing materials is better.In addition, this seminar recent work finds, compared with traditional borosilicate system seal glass (not containing NiO), adopts and adds the sealing property that NiO can significantly improve seal, sealing materials.Fig. 1 is traditional borosilicate system seal glass (not containing NiO) and Cr
2o
3the ultraviolet spectrogram of powder at high temperature solid state reaction product.Fig. 2 is the ultraviolet spectrogram of seal glass under parallel laboratory test condition of interpolation 5% NiO.Fig. 3 is the ultraviolet spectrogram of seal glass under parallel laboratory test condition of interpolation 10% NiO.Fig. 4 is the ultraviolet spectrogram of seal glass under parallel laboratory test condition of interpolation 18% NiO.Fig. 5 is the ultraviolet spectrogram of seal glass under parallel laboratory test condition of interpolation 25% NiO.Fig. 6 is the ultraviolet spectrogram of seal glass under parallel laboratory test condition of interpolation 30% NiO.Can clearly see from the contrast of five figure, the chemical stability of sealing-in seal glass increases trend with the raising of NiO addition.Fig. 7 is the Alysis of Thermal Exponsion Coefficient figure of seal glass under parallel laboratory test condition that different Ni O adds.Can obviously be found out by the contrast of Fig. 7, the softening temperature of sealing-in seal glass and glass transition point reduce with the raising of NiO addition, are applicable to the operating temperature range of intermediate temperature fuel cell.
The present invention relates generally to Solid Oxide Fuel Cell (SOFC) field, but is not limited to SOFC, can also be used for the sealing-in between metalloid and pottery.
The foregoing is only preferred embodiment of the present invention, all equalizations done according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.
Claims (6)
1. a sealing glass ceramic, is characterized in that: raw material consists of SiO
2, MO and NiO, its mol ratio is 45-50:20-30:25-30; The wherein mixture of MO to be mol ratio be CaO and SrO of 1:1.
2. prepare a method for sealing glass ceramic as claimed in claim 1, it is characterized in that: comprise the following steps:
(1) raw material is mixed; Found through 1300-1400 DEG C, soaking time 1-4 hour; To the glass metal melted, carry out chilling, obtain glass frit; Then, pulverized by glass frit, grinding, obtains glass powder after sieving;
(2) by glass powder and binding agent, dispersion agent and solvent form slurry, in ball mill, ball milling is dispersed; Flow casting molding, seasoning, is then cut into the base substrate of desired shape, makes glass sealing material.
3. the preparation method of sealing glass ceramic according to claim 2, is characterized in that: the binding agent of described step (2) is the mixture of one or more in epoxy resin, methylcellulose gum, polyvinyl butyral acetal, polyvinyl alcohol.
4. the preparation method of sealing glass ceramic according to claim 2, is characterized in that: the dispersion agent of described step (2) is the mixture of one or more in fish oil, polyacrylic acid, polyvinyl alcohol, polyacrylamide.
5. the preparation method of sealing glass ceramic according to claim 2, is characterized in that: the solvent of described step (2) is the mixture of one or more in water, ethanol, Virahol, propyl carbinol, toluene, dimethylbenzene, acetone.
6. the using method of a sealing glass ceramic as claimed in claim 1, it is characterized in that: glass sealing material is placed in and treats sealing-in position, with the ramp of 1-5 DEG C/min in electric furnace, 400-500 DEG C of insulation 0.5-2 hour, then with the ramp of 1-5 DEG C/min to 750-850 DEG C of Crystallizing treatment 0.5-2 hour, namely complete sealing-in.
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Families Citing this family (5)
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|---|---|---|---|---|
| CN104926132B (en) * | 2015-06-10 | 2017-07-04 | 福州大学 | A kind of Ce and Hf codoping modified sealing glass ceramic |
| CN106219982B (en) * | 2016-07-26 | 2019-04-23 | 浙江宇清热工科技股份有限公司 | For the glaze and its application method of combination between a kind of devitrified glass |
| JP6429848B2 (en) * | 2016-12-09 | 2018-11-28 | 日本碍子株式会社 | Electrochemical cell |
| CN108383389A (en) * | 2018-05-04 | 2018-08-10 | 福州大学 | A kind of high boron sealing glass ceramic and its preparation and application containing NiO |
| CN113336479B (en) * | 2021-05-21 | 2023-07-11 | 景德镇陶瓷大学 | Cordierite-based microcrystalline glass high-temperature binder and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101148322A (en) * | 2007-06-29 | 2008-03-26 | 清华大学 | Microcrystal glass sealing material used for solid oxide fuel battery and sealing method thereof |
| CN102503136A (en) * | 2011-11-14 | 2012-06-20 | 中国科学院上海硅酸盐研究所 | Sealing material for medium/low-temperature solid oxide fuel battery and preparation method thereof |
| CN103030278A (en) * | 2013-01-08 | 2013-04-10 | 福州大学 | Glass sealing material, as well as preparation and using methods thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPWO2004031088A1 (en) * | 2002-10-07 | 2006-02-02 | 日本板硝子株式会社 | Glass frit for sealing |
| JP5128203B2 (en) * | 2007-08-22 | 2013-01-23 | 日本山村硝子株式会社 | Glass composition for sealing |
| JP5301587B2 (en) * | 2011-02-24 | 2013-09-25 | 株式会社ノリタケカンパニーリミテド | Non-alkali glass-based sealing material for solid oxide fuel cells |
-
2013
- 2013-05-27 CN CN201310200396.XA patent/CN103288349B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101148322A (en) * | 2007-06-29 | 2008-03-26 | 清华大学 | Microcrystal glass sealing material used for solid oxide fuel battery and sealing method thereof |
| CN102503136A (en) * | 2011-11-14 | 2012-06-20 | 中国科学院上海硅酸盐研究所 | Sealing material for medium/low-temperature solid oxide fuel battery and preparation method thereof |
| CN103030278A (en) * | 2013-01-08 | 2013-04-10 | 福州大学 | Glass sealing material, as well as preparation and using methods thereof |
Non-Patent Citations (3)
| Title |
|---|
| BaO-Al2O3-B2O3系密封玻璃的结构与性质;曾凡蓉等;《无机化学学报》;20080531;第24卷(第5期);第808-812页 * |
| 张腾等.固体氧化物燃料电池封接玻璃的研究:成分与性能.《功能材料》.2010,第221-224页. * |
| 毛宗强等.低温固体氧化物燃料电池.《低温固体氧化物燃料电池》.上海科学技术出版社,2013,第224页. * |
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