CN103553334A - MnO2-containing glass sealing material as well as preparation and use methods thereof - Google Patents
MnO2-containing glass sealing material as well as preparation and use methods thereof Download PDFInfo
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- CN103553334A CN103553334A CN201310501671.1A CN201310501671A CN103553334A CN 103553334 A CN103553334 A CN 103553334A CN 201310501671 A CN201310501671 A CN 201310501671A CN 103553334 A CN103553334 A CN 103553334A
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- 239000011521 glass Substances 0.000 title claims abstract description 117
- 239000003566 sealing material Substances 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title abstract 14
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims description 30
- 238000000498 ball milling Methods 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 239000000446 fuel Substances 0.000 claims description 15
- 238000009413 insulation Methods 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 12
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 9
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 9
- 238000005266 casting Methods 0.000 claims description 8
- 238000002425 crystallisation Methods 0.000 claims description 8
- 230000008025 crystallization Effects 0.000 claims description 8
- 235000011194 food seasoning agent Nutrition 0.000 claims description 8
- 238000000465 moulding Methods 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 5
- 229920000609 methyl cellulose Polymers 0.000 claims description 5
- 239000001923 methylcellulose Substances 0.000 claims description 5
- 229920002125 Sokalan® Polymers 0.000 claims description 4
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 4
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 claims description 4
- 239000003822 epoxy resin Substances 0.000 claims description 4
- 235000021323 fish oil Nutrition 0.000 claims description 4
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 4
- 229920002401 polyacrylamide Polymers 0.000 claims description 4
- 239000004584 polyacrylic acid Substances 0.000 claims description 4
- 229920000647 polyepoxide Polymers 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 3
- 238000000354 decomposition reaction Methods 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 238000010791 quenching Methods 0.000 claims description 3
- 230000000171 quenching effect Effects 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 abstract description 9
- 239000005394 sealing glass Substances 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 2
- 229910011255 B2O3 Inorganic materials 0.000 abstract 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 238000009533 lab test Methods 0.000 description 14
- 239000011651 chromium Substances 0.000 description 13
- 230000009477 glass transition Effects 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- 238000003746 solid phase reaction Methods 0.000 description 8
- 238000010671 solid-state reaction Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 6
- 230000009257 reactivity Effects 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 238000006557 surface reaction Methods 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000012634 fragment Substances 0.000 description 5
- 239000000156 glass melt Substances 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229910000599 Cr alloy Inorganic materials 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical group CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 230000008646 thermal stress Effects 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000005343 cylinder glass Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- AFYAQDWVUWAENU-UHFFFAOYSA-H nickel(2+);diphosphate Chemical compound [Ni+2].[Ni+2].[Ni+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O AFYAQDWVUWAENU-UHFFFAOYSA-H 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000005365 phosphate glass Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000011158 quantitative evaluation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910001256 stainless steel alloy Inorganic materials 0.000 description 1
- 238000005382 thermal cycling Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 1
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- Glass Compositions (AREA)
Abstract
The invention discloses a MnO2-containing glass sealing material as well as preparation and use methods thereof. The raw material composition of the MnO2-containing glass sealing material comprises B2O3, Al2O3, SiO2, RO (one or a mixture of more of MgO, CaO, SrO and BaO) and MnO2, wherein the molar ratio of the components is (0-10):(0-5):(25-60):(20-50):(5-30). Mn ions of a mixed valence state (Mn<2+> and Mn<3+>, and the relative contents of Mn ions of different valence states are closely related to the amount of the added MnO2) are introduced by adding the MnO2 into the sealing glass, and the regulation and control over the high-temperature chemical stability of the sealing glass are thermodynamically realized; meanwhile, the softening temperature of the sealing glass can also be reduced and the sinterability of the sealing glass can be improved by virtue of the added MnO2. The preparation raw materials are simple and readily available, the process is stable, and the obtained invert glass network structure is low in cost, has a simple and feasible process and reaches practical and industrial conditions.
Description
Technical field
The invention belongs to field of solid oxide fuel, be specifically related to a kind of containing MnO
2glass sealing material and preparation and application thereof.
Background technology
The advantages such as Solid Oxide Fuel Cell (SOFC) adopts soild oxide (pottery) ionogen, and at high temperature operation, has generating efficiency high, and the cost of material is low, fuel tolerance strong (as methane, coal gas, methyl alcohol, alcohol, oil liquefied gas etc.).But the subject matter that faces of exploitation SOFC is that at high temperature how fuel gas and oxic gas effectively completely cut off and sealing-in.Due to the working temperature high (700～750 ℃) of battery, select suitable seal, sealing materials and sealing technology 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, investigator has adopted both at home and abroad:
1. to carrying out preoxidation containing Cr alloy linker, to reduce seal, sealing materials and the surface reaction that contains Cr alloy;
2. to armor coated containing Cr alloy linker, to limit the diffusion of Cr;
3. the Loehman that controls surface reaction ，Ru U.S. Sandia National Laboratory by improving the formula of seal glass also attempts adding to glass basis the Cr of saturation concentration
2o
3to suppress the diffusion of Cr;
4. utilize alkalimetal oxide (as Na
2o and K
2o) replace the methods such as alkaline earth metal oxide that easily react, but above method all fails to satisfactorily resolve the sealing-in Problem of Failure that surface reaction causes.
On seal, sealing materials, the glass system of research mainly concentrates on phosphorus system, boron system and silicate.(1) series of phosphate: under SOFC working temperature, phosphoric acid salt volatilizees easily and anode generation surface reaction, forms nickelous phosphate and zirconium phosphate etc., reduces anode active.Meanwhile, the stability of the crystal that phosphate glass forms in moist fuel atmosphere is also very undesirable.(2) borate salt system: B
2o
3interpolation can promote the reduction of glass transition point, improve the formation ability of glass, but B
2o
3remarkable volatilization under hot conditions is restricting the application of borate-based glass in SOFC seal, sealing materials.Research find this be glass because volatilization causes obvious weightlessness, and the reaction at the interface occurring is also clearly.(3) silicate systems: comparatively speaking, the volatility of silicate-based glasses material a little less than, there is stronger sealing-in stability.In order to obtain the mobility of enough materials, people attempt adopting and add various additives to improve sealing-in effect.In recent years, it is found that adopting mixed type glass is a direction that can obtain better sealing-in effect.Wherein borosilicate is the system that people comparatively pay close attention to, by regulation and control B
2o
3/ SiO
2ratio can obtain required glass transition point and glass softening point.
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 germinating and the expansion of crackle, so that the defect of sealing-in ultimate failure, research both at home and abroad drops into the self-healing seal, sealing materials that great effort exploitation at high temperature can long term maintenance vitreous state, attempts viscosity by glassy phase and flows and discharge the thermal stresses of seal interface accumulation.Yet, for improving the network ligand ion (RuIIA family) of seal glass viscosity, easily react under SOFC working temperature with containing Cr alloy linker, generate as BaCrO
4, SrCrO
4and CaCrO
4deng thering is high thermal expansivity (18 ~ 20 * 10
-6/ K) product, causes the coefficient of thermal expansion mismatch with other elements of seal interface again, destroys sealing-in bonding force, seriously restricts the work-ing life of seal, sealing materials and SOFC, especially in the stability of Thermal Cycling.
Summary of the invention
In order to address the above problem, the invention provides a kind of containing MnO
2glass sealing material and preparation and application thereof, by adding MnO
2to the Mn ion (Mn that introduces mixed valence in seal glass
2+with Mn
3+, and different valence state Mn ion relative content and MnO
2addition closely related), from thermodynamics, the stability at elevated temperature of seal glass is realized to regulation and control; Meanwhile, MnO
2add the softening temperature that can also reduce seal glass, improve its coking property.
For achieving the above object, the present invention adopts following technical scheme:
A kind of containing MnO
2the raw material of glass sealing material consist of B
2o
3, Al
2o
3, SiO
2, RO and MnO
2, its mol ratio is 0 ~ 10:0 ~ 5:25 ~ 60:20 ~ 50:5 ~ 30; Wherein RO is one or more the mixture in MgO, CaO, SrO, BaO.
Preparation method comprises the following steps:
(1) raw material is mixed by proportioning ball milling; At 1100 ℃, carry out, after carbonate decomposition, at 1400-1500 ℃, founding insulation 2-5 hour; The glass metal melting is poured in cold water and carried out quenching, obtain glass frit; Glass frit is pulverized, ground or ball milling, after sieving, obtain glass powder;
(2) glass powder of step (1) is incubated to 2-5 hour at 700-750 ℃, to regulate Mn
2+with Mn
3+relative content;
(3) by the glass powder of step (2) and dispersion agent, binding 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.
Described binding agent comprises epoxy resin, methylcellulose gum, polyvinyl butyral acetal, the mixture of one or more of polyvinyl alcohol.
Described dispersion agent comprises one or more mixture of fish oil, polyacrylic acid, polyvinyl alcohol, polyacrylamide.
Described solvent comprises one or more mixture of water, ethanol, Virahol, propyl carbinol, toluene, dimethylbenzene, acetone.
Glass sealing material is placed in and treats sealing-in position, speed with 1-5 ℃/min in electric furnace heats up, at 400-500 ℃ of insulation 0.5-2 hour, with 3 ℃/min, be heated to 700-750 ℃ of crystallization again and process 2-5 hour, with the speed of 1-3 ℃/min, be warming up to again the working temperature of Solid Oxide Fuel Cell, complete sealing-in.
Remarkable advantage of the present invention is:
(1) by adding MnO
2to the Mn ion (Mn that introduces mixed valence in seal glass
2+with Mn
3+, and different valence state Mn ion relative content and MnO
2addition closely related), from thermodynamics, the stability at elevated temperature of seal glass is realized to regulation and control;
(2) MnO
2add the softening temperature that can also reduce seal glass, improve its coking property;
(3) raw materials that the present invention selects is cheap, and source channel is various, process stabilizing.Selecting corresponding oxide compound is source material, and they are evenly mixed, and in fusing and subsequent heat treatment, remains a high proportion of mixing and distribution state, can prepare with SiO
2for the inverse glass network structure of main body, and excellent performance, be applicable to Solid Oxide Fuel Cells sealing-in, reached practical and industrialized condition.
Accompanying drawing explanation
Fig. 1 is that traditional borosilicate is that seal glass is not (containing MnO
2) and Cr
2o
3powder carries out the ultraviolet spectrogram of the reaction product of solid state reaction after 24 hours at 750 ℃.
Fig. 2 is for adding 5% MnO
2the ultraviolet spectrogram of seal glass under parallel laboratory test condition.
Fig. 3 is for adding 10% MnO
2the ultraviolet spectrogram of seal glass under parallel laboratory test condition.
Fig. 4 is for adding 20%MnO
2the ultraviolet spectrogram of seal glass under parallel laboratory test condition.
Fig. 5 is for adding 25% MnO
2the ultraviolet spectrogram of seal glass under parallel laboratory test condition.
Fig. 6 is for adding 30% MnO
2the ultraviolet spectrogram of seal glass under parallel laboratory test condition.
Fig. 7 is different MnO
2the Mn of the seal glass adding under parallel laboratory test condition
3+/ (Mn
2++ Mn
3+).
Fig. 8 is different MnO
2the thermal expansion curve of the seal glass adding under parallel laboratory test condition.
Embodiment
A kind of containing MnO
2the raw material of seal glass consist of B
2o
3, Al
2o
3, SiO
2, one or more the mixture in MO(MgO, CaO, SrO, BaO) and MnO
2, its mol ratio is 0 ~ 10:0 ~ 5:25 ~ 60:20 ~ 50:5 ~ 30.
Said method comprising the steps of:
(1) preparation of seal glass: raw material is mixed; At 1100 ℃, carry out carbonate decomposition, at 1400 ~ 1500 ℃, found soaking time 2-5 hour; The glass metal part melting is poured in stainless steel mould, obtained the right cylinder glass of certain size, a remaining part is poured in cold water and is carried out quenching, obtains glass frit; Then, glass frit is pulverized, ground or ball milling, after sieving, obtain glass powder;
(2) glass powder of above-mentioned acquisition is incubated to 2-5 hour at 700-750 ℃, obtains the glass system that different Mn ionic valence conditions mix;
(3) preparation of glass idiosome: the glass powder that step (2) was processed 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 (3) comprises epoxy resin, methylcellulose gum, polyvinyl butyral acetal, one or more of polyvinyl alcohol.The dispersion agent of described step (3) comprises one or more of fish oil, polyacrylic acid, polyvinyl alcohol, polyacrylamide.The solvent of described step (3) is one or more of water, ethanol, Virahol, propyl carbinol, toluene, dimethylbenzene, acetone.
The using method of glass sealing material, that glass sealing material is placed in and treats sealing-in position, speed with 1-5 ℃/min in electric furnace heats up, at 400-500 ℃ of insulation 0.5-2 hour, with 3 ℃/min, be heated to 700-750 ℃ of crystallization again and process 2-5 hour, with the speed of 1-3 ℃/min, be warming up to again the working temperature of Solid Oxide Fuel Cell, complete sealing-in.
Table 1 is the sealing glass composition 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, MnO
2), with planetary ball mill ball milling, within 24 hours, mix; Then powder is put into crucible, be placed in the air atmosphere of chamber type electric resistance furnace, with 3 ℃/min, be heated to 1500 ℃, be incubated 2 hours; Then, take out crucible, pour melt in deionized water chilling, the dry fragment that obtains glass melt; Grind, cross 100 mesh sieves.Glass powder and polyvinyl alcohol, fish oil, ethanol and toluene (weight ratio is followed successively by 80%, 6%, 2%, 10%, 2%) 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, speed with 2 ℃/min in electric furnace heats up, and 450 ℃ of insulations 1 hour, then is heated to 750 ℃ of crystallization processing 2 hours with 3 ℃/min, with the speed of 3 ℃/min, be warming up to again the working temperature of Solid Oxide Fuel Cell, complete sealing-in.Fig. 2 shows, adds 5% MnO
2seal glass and Cr
2o
3powder carries out the reactivity of solid state reaction after 24 hours for not containing accordingly MnO at 750 ℃
2seal glass 35%.Melt after insulation is poured in the stainless steel grinding tool after preheating, obtained Φ=10mm, the glass cylinder of d=25mm with the heating rate test of 10 ℃/min, obtains glass transition point and softening temperature on NETZSCH DIL 402EP thermal dilatometer.Fig. 7 shows, adds 5%MnO
2the Mn of seal glass
3+/ (Mn
2++ Mn
3+) be 0.6.Fig. 8 shows, adds 5%MnO
2the glass transition point Tg of seal glass be 664 ℃, softening temperature is 729 ℃.
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, MnO
2), with planetary ball mill ball milling, within 24 hours, mix; Then powder is put into platinum crucible, be placed in the air atmosphere of chamber type electric resistance furnace, with 3 ℃/min, be heated to 1450 ℃, be incubated 2 hours; Then, take out crucible, pour melt in deionized water chilling, the dry fragment that obtains glass melt; Grind, cross 100 mesh sieves.This glass powder is mixed into slurry by obtained glass powder and methylcellulose gum, polyvinyl alcohol, propyl carbinol and acetone (weight ratio is followed successively by 84%, 3%, 1%, 8%, 4%), 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, speed with 2 ℃/min in electric furnace heats up, and 500 ℃ of insulations 1 hour, is heated to 730 ℃ of crystallization processes 2 hours with 3 ℃/min, with the speed of 3 ℃/min, be warming up to again the working temperature of Solid Oxide Fuel Cell, complete sealing-in.This example is preferably to form.Fig. 3 shows, adds 10% MnO
2seal glass and Cr
2o
3powder carries out the reactivity of solid state reaction after 24 hours for not containing accordingly MnO at 750 ℃
2seal glass 42%.Melt after insulation is poured in the stainless steel grinding tool after preheating, obtained Φ=10mm, the glass cylinder of d=25mm with the heating rate test of 10 ℃/min, obtains glass transition point and softening temperature on NETZSCH DIL 402EP thermal dilatometer.Fig. 7 shows, adds 10%MnO
2the Mn of seal glass
3+/ (Mn
2++ Mn
3+) be 0.4.Fig. 8 shows, adds 10%MnO
2the glass transition point Tg of seal glass be 657 ℃, softening temperature is 717 ℃.
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, MnO
2), with planetary ball mill ball milling, within 24 hours, mix; Then powder is put into crucible, be placed in the air atmosphere of chamber type electric resistance furnace, with 3 ℃/min, be heated to 1450 ℃, be incubated 2 hours; Then, take out crucible, pour melt in deionized water chilling, the dry fragment that obtains glass melt; Grind, cross 100 mesh sieves.Obtained glass powder and methylcellulose gum, polyvinyl alcohol, propyl carbinol and acetone (weight ratio is followed successively by 81%, 4%, 2%, 9%, 4%) 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, speed with 3 ℃/min in electric furnace heats up, and 450 ℃ of insulations 1 hour, then is heated to 720 ℃ of crystallization processing 2 hours with 3 ℃/min, with the speed of 3 ℃/min, be warming up to again the working temperature of Solid Oxide Fuel Cell, complete sealing-in.Fig. 4 shows, adds 20% MnO
2seal glass and Cr
2o
3powder carries out the reactivity of solid state reaction after 24 hours for not containing accordingly MnO at 750 ℃
2seal glass 60%.Melt after insulation is poured in the stainless steel grinding tool after preheating, obtained Φ=10mm, the glass cylinder of d=25mm with the heating rate test of 10 ℃/min, obtains glass transition point and softening temperature on NETZSCH DIL 402EP thermal dilatometer.Fig. 7 shows, adds 20%MnO
2the Mn of seal glass
3+/ (Mn
2++ Mn
3+) be 0.2.Fig. 8 shows, adds 20%MnO
2the glass transition point Tg of seal glass be 651 ℃, softening temperature is 704 ℃.
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, SiO
2, Al
2o
3, B
2o
3, MnO
2), with planetary ball mill ball milling, within 24 hours, mix; Then powder is put into crucible, be placed in the air atmosphere of chamber type electric resistance furnace, with 3 ℃/min, be heated to 1400 ℃, be incubated 2 hours; Then, take out crucible, pour melt in deionized water chilling, the dry fragment that obtains glass melt; Grind, cross 100 mesh sieves, obtain glass powder.Obtained glass powder and epoxy resin, polyacrylamide, Virahol and toluene (weight ratio is followed successively by 81%, 3%, 2%, 10%, 4%) 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, speed with 2 ℃/min in electric furnace heats up, and 500 ℃ of insulations 1 hour, then is heated to 700 ℃ of crystallization processing 2 hours with 3 ℃/min, with the speed of 3 ℃/min, be warming up to again the working temperature of Solid Oxide Fuel Cell, complete sealing-in.This example is preferably to form.Fig. 5 shows, adds 25% MnO
2seal glass and Cr
2o
3powder carries out the reactivity of solid state reaction after 24 hours for not containing accordingly MnO at 750 ℃
2seal glass 31%.Melt after insulation is poured in the stainless steel grinding tool after preheating, obtained Φ=10mm, the glass cylinder of d=25mm with the heating rate test of 10 ℃/min, obtains glass transition point and softening temperature on NETZSCH DIL 402EP thermal dilatometer.Fig. 7 shows, adds 25%MnO
2the Mn of seal glass
3+/ (Mn
2++ Mn
3+) be 0.8.Fig. 8 shows, adds 25%MnO
2the glass transition point T of seal glass
gbe 650 ℃, softening temperature is 688 ℃.
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, MnO
2), with planetary ball mill ball milling, within 24 hours, mix; Then powder is put into crucible, be placed in the air atmosphere of chamber type electric resistance furnace, with 3 ℃/min, be heated to 1400 ℃, be incubated 2 hours; Then, take out crucible, pour melt in deionized water chilling, the dry fragment that obtains glass melt; Grind, cross 100 mesh sieves, obtain glass powder.Obtained glass powder and polyvinyl butyral acetal, polyacrylic acid, Virahol and acetone (weight ratio is followed successively by 82%, 2%, 2%, 10%, 4%) 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, speed with 2 ℃/min in electric furnace heats up, and 480 ℃ of insulations 1 hour, then is heated to 700 ℃ of crystallization processing 2 hours with 3 ℃/min, with the speed of 3 ℃/min, be warming up to again the working temperature of Solid Oxide Fuel Cell, complete sealing-in.Fig. 6 shows, adds 30% MnO
2seal glass and Cr
2o
3powder carries out the reactivity of solid state reaction after 24 hours for not containing accordingly MnO at 750 ℃
2seal glass 26%.Melt after insulation is poured in the stainless steel grinding tool after preheating, obtained Φ=10mm, the glass cylinder of d=25mm with the heating rate test of 10 ℃/min, obtains thermal expansivity and softening temperature on NETZSCH DIL 402EP thermal dilatometer.Fig. 7 shows, adds 30%MnO
2the Mn of seal glass
3+/ (Mn
2++ Mn
3+) be 0.9.Fig. 8 shows, adds 30%MnO
2the glass transition point T of seal glass
gbe 645 ℃, softening temperature is 683 ℃.
The present invention has obtained the seal glass with stability at elevated temperature and sealing property by above-mentioned enforcement.Its significant effect embodies a concentrated reflection of the raising aspect of stability at elevated temperature, its principle be in seal glass mixed valence ion especially lower valency ion in surface reaction process, serve as the role of competing reaction, from thermodynamics aspect, effectively reduce reacting of network part and metallic matrix.To seal, sealing materials and Cr
2o
3powder at high temperature the product of solid state reaction by ultraviolet spectroscopy Cr(VI) absorption intensity, chemical stability that can quantitative evaluation material, the number of pages that was published in < < Journal of Power Sources > > referring to this seminar in 2010 is at 6795 to 6797 article.Reactivity is lower, shows that the stability at elevated temperature of seal, sealing materials is better.，Ben seminar recent work is found in addition, with traditional borosilicate be that seal glass is (containing MnO
2) compare, add MnO
2glass in surface reaction process, present unique reaction mechanism.Fig. 1 is that traditional borosilicate is that seal glass is not (containing MnO
2) and Cr
2o
3powder is the ultraviolet spectrogram of solid state reaction product at high temperature.Fig. 2 is for adding 5% MnO
2the ultraviolet spectrogram of seal glass under parallel laboratory test condition.Fig. 3 is for adding 10% MnO
2the ultraviolet spectrogram of seal glass under parallel laboratory test condition.Fig. 4 is for adding 20% MnO
2the ultraviolet spectrogram of seal glass under parallel laboratory test condition.Fig. 5 is for adding 25% MnO
2the ultraviolet spectrogram of seal glass under parallel laboratory test condition.Fig. 6 is for adding 30% MnO
2the ultraviolet spectrogram of seal glass under parallel laboratory test condition.From the contrast of five figure, can see the chemical stability of seal glass and MnO
2addition is closely related.Fig. 7 is different MnO
2the Mn of the seal glass adding under parallel laboratory test condition
3+/ (Mn
2++ Mn
3+).Contrast by Fig. 6 and Fig. 7 can be found out Mn
3+/ (Mn
2++ Mn
3+) with the corresponding relation of seal glass chemical stability.Fig. 8 is different MnO
2the Alysis of Thermal Exponsion Coefficient figure of the seal glass adding under parallel laboratory test condition.As shown in Figure 8, the softening temperature of sealing-in seal glass and glass transition point are with MnO
2the raising of addition and reducing, is 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 for the sealing-in between metalloid and pottery.
The foregoing is only preferred embodiment of the present invention, all equalizations of doing 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 (7)
1. one kind contains MnO
2glass sealing material, it is characterized in that: raw material consists of B
2o
3, Al
2o
3, SiO
2, RO and MnO
2, its mol ratio is 0 ~ 10:0 ~ 5:25 ~ 60:20 ~ 50:5 ~ 30; Wherein RO is one or more the mixture in MgO, CaO, SrO, BaO.
2. according to claim 1 containing MnO
2glass sealing material, it is characterized in that: raw material B
2o
3, Al
2o
3, SiO
2, RO and MnO
2mol ratio be 5 ~ 10:0 ~ 5:40 ~ 60:25 ~ 40:10 ~ 25.
3. prepare as claimed in claim 1 containing MnO for one kind
2the method of glass sealing material, it is characterized in that: comprise the following steps:
(1) raw material is mixed by proportioning ball milling; At 1100 ℃, carry out, after carbonate decomposition, at 1400-1500 ℃, founding insulation 2-5 hour; The glass metal melting is poured in cold water and carried out quenching, obtain glass frit; Glass frit is pulverized, ground or ball milling, after sieving, obtain glass powder;
(2) glass powder of step (1) is incubated to 2-5 hour at 700-750 ℃, to regulate Mn
2+with Mn
3+relative content;
(3) by the glass powder of step (2) and dispersion agent, binding 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.
4. according to claim 3 containing MnO
2the preparation method of glass sealing material, it is characterized in that: the binding agent of described step (3) comprises epoxy resin, methylcellulose gum, polyvinyl butyral acetal, the mixture of one or more of polyvinyl alcohol.
5. according to claim 3 containing MnO
2the preparation method of glass sealing material, it is characterized in that: the dispersion agent of described step (3) comprises one or more mixture of fish oil, polyacrylic acid, polyvinyl alcohol, polyacrylamide.
6. according to claim 3 containing MnO
2the preparation method of glass sealing material, it is characterized in that: the solvent of described step (3) comprises one or more mixture of water, ethanol, Virahol, propyl carbinol, toluene, dimethylbenzene, acetone.
One kind as claimed in claim 1 containing MnO
2the using method of glass sealing material, it is characterized in that: glass sealing material is placed in and treats sealing-in position, speed with 1-5 ℃/min in electric furnace heats up, at 400-500 ℃ of insulation 0.5-2 hour, with 3 ℃/min, be heated to 700-750 ℃ of crystallization again and process 2-5 hour, with the speed of 1-3 ℃/min, be warming up to again the working temperature of Solid Oxide Fuel Cell, complete sealing-in.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106430979A (en) * | 2016-11-01 | 2017-02-22 | 福州大学 | Mn-containing low-temperature seal glass as well as preparation method and use method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102906046A (en) * | 2010-04-01 | 2013-01-30 | 法国原子能及替代能源委员会 | Glass-ceramic compositions for joints of appliances operating at high temperatures, and assembly method using said compositions |
-
2013
- 2013-10-23 CN CN201310501671.1A patent/CN103553334B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102906046A (en) * | 2010-04-01 | 2013-01-30 | 法国原子能及替代能源委员会 | Glass-ceramic compositions for joints of appliances operating at high temperatures, and assembly method using said compositions |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106430979A (en) * | 2016-11-01 | 2017-02-22 | 福州大学 | Mn-containing low-temperature seal glass as well as preparation method and use method thereof |
| CN106430979B (en) * | 2016-11-01 | 2019-03-12 | 福州大学 | A kind of low temperature sealing glass and its preparation and application containing Mn |
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