CN115959832A - BaO-containing microcrystal sealing glass for solid oxide fuel cell and preparation and use methods thereof - Google Patents
BaO-containing microcrystal sealing glass for solid oxide fuel cell and preparation and use methods thereof Download PDFInfo
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- CN115959832A CN115959832A CN202310011755.0A CN202310011755A CN115959832A CN 115959832 A CN115959832 A CN 115959832A CN 202310011755 A CN202310011755 A CN 202310011755A CN 115959832 A CN115959832 A CN 115959832A
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- 239000005394 sealing glass Substances 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 19
- 239000013081 microcrystal Substances 0.000 title claims abstract description 13
- 239000000446 fuel Substances 0.000 title claims abstract description 12
- 239000007787 solid Substances 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000011521 glass Substances 0.000 claims abstract description 48
- 238000010438 heat treatment Methods 0.000 claims abstract description 23
- 239000000843 powder Substances 0.000 claims abstract description 22
- 238000007789 sealing Methods 0.000 claims abstract description 19
- 239000010935 stainless steel Substances 0.000 claims abstract description 10
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 10
- 238000010791 quenching Methods 0.000 claims abstract description 6
- 230000000171 quenching effect Effects 0.000 claims abstract description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 4
- 238000002844 melting Methods 0.000 claims abstract description 3
- 230000008018 melting Effects 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims description 15
- 239000002002 slurry Substances 0.000 claims description 13
- 238000000227 grinding Methods 0.000 claims description 11
- 239000011230 binding agent Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 239000001856 Ethyl cellulose Substances 0.000 claims description 5
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 5
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 5
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims description 5
- 229920001249 ethyl cellulose Polymers 0.000 claims description 5
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 5
- 229940116411 terpineol Drugs 0.000 claims description 5
- 238000000498 ball milling Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 2
- 238000010309 melting process Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims 1
- 239000000565 sealant Substances 0.000 abstract description 7
- 230000007774 longterm Effects 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 238000007493 shaping process Methods 0.000 abstract 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- 239000012634 fragment Substances 0.000 description 8
- 239000000156 glass melt Substances 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000010965 430 stainless steel Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000004455 differential thermal analysis Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000005337 ground glass Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002241 glass-ceramic Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- -1 oxygen ion Chemical class 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000005368 silicate glass Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000005382 thermal cycling Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Glass Compositions (AREA)
- Fuel Cell (AREA)
Abstract
The invention discloses a microcrystal sealing glass of BaO-containing solid oxide fuel cell and its preparation and application method, the prepared microcrystal glass component is BaO, mgO, al 2 O 3 、B 2 O 3 And SiO 2 . The BaO-containing microcrystal sealing glass powder matched with the SOFC component is successfully prepared by a melting quenching method, and the NiO-YSZ anode supporting type SOFC and the stainless steel connector are sealed by means of shaping and heat treatment after glass sealant is prepared. The microcrystalline glass sealing element is applied to medium-temperature SOFC (solid oxide fuel cell)Has good long-term physical and chemical stability under the working conditions. The invention ensures the operation stability of the medium-temperature SOFC under the working condition and has better application prospect.
Description
Technical Field
The invention relates to the field of fuel cells, in particular to BaO-containing microcrystal sealing glass for a solid oxide fuel cell and a preparation method and a use method thereof.
Background
A Solid Oxide Fuel Cell (SOFC) is a power generation device that converts chemical energy in fuel and oxidant gases directly into electrical energy by oxygen ion or proton conduction. The SOFC single cell has limited voltage and power, and needs to be connected in series, parallel or series-parallel to form a cell stack to improve the power generation efficiency. The flat SOFC battery has the characteristics of thin thickness and high energy density, and the main defects of the flat SOFC battery are large sealing area and difficult sealing. Silicate-based microcrystalline glass is suitable as a sealing material for high-temperature SOFC. However, as the operating temperature decreases, the sealing performance of silicate microcrystalline glass deteriorates, and the addition of an alkaline earth metal oxide modifier to silicate-based glass can significantly improve the sealing performance in medium and low temperature regions. For example, the thermal properties of the microcrystalline sealing glass can be regulated by adding BaO. With the addition of BaO, the Coefficient of Thermal Expansion (CTE) of the glass-ceramic increases significantly. An increase in the BaO content increases the amount of nonbridging oxygens in the glass matrix and lowers the glass transition temperature (T) g ) And glass softening temperature (T) s ) And improving the wettability of the glass and the SOFC component. The silicate glass taking BaO as a modifier can reduce the crystallization temperature (T) of the glass c ) Increasing the crystallization at operating temperature, the presence of crystalline phases with CTE close to that of the glass matrix, improves the bond strength of the high temperature seal, while the self-healing property of slight softening of the residual glass phase avoids structural damage from thermal stress during thermal cycling (International Journal of Energy Research, 2021, 91 (8): P20559-20582).
In conclusion, the invention prepares and uses BaO-MgO-Al 2 O 3 -B 2 O 3 -SiO 2 The microcrystal seals the glass powder, and is molded and thermally treated after being prepared into glass sealant, so as to ensure the long-time running stability of the SOFC. Compared with the prior art, the method has obvious progress and better application prospect.
Disclosure of Invention
The invention provides a BaO-containing SOFC microcrystalline sealing glass and a preparation method and a use method thereof.
In order to realize the purpose, the invention is implemented by the following technical scheme:
the BaO-containing SOFC microcrystal sealing glass is prepared with BaO, mgO and Al as material 2 O 3 、B 2 O 3 And SiO 2 Prepared according to the molar ratio of (30) - (40): (10) - (20): 1~5): 8) - (12): 35) - (55).
The method for preparing and using the BaO-containing SOFC microcrystalline sealing glass comprises the following steps:
(1) Uniformly mixing a certain amount of raw materials and then melting; quenching the melted glass liquid to obtain a glass frit; crushing, grinding or ball-milling the glass frit, and sieving to obtain glass powder;
(2) Mixing glass powder and an organic binder into slurry, and performing ball milling or grinding until the slurry is uniformly dispersed to obtain a raw material of the glass sealing element;
(3) Placing the glass sealing element raw material between the flat SOFC and the stainless steel connector material, slowly heating and drying, and then carrying out heat treatment to obtain the sealing.
The melting process in the step (1) is carried out at 1300 to 1400 ℃ for 1~2 hours.
The standard test sieve selected in the step (1) is 325 meshes, and the grain diameter of the sieved glass powder is less than or equal to 45 mu m.
The binder in the step (2) is a mixture of ethyl cellulose and terpineol, and the mass ratio is 4.
The mass ratio of the glass powder to the binder in the step (2) is 2.5 to 3.5.
And (3) keeping the temperature of the drying process at 100-150 ℃ for 1~2 hours.
The flat SOFC in the step (3) is a NiO-YSZ anode supporting type SOFC, and the stainless steel connector is SUS430 type stainless steel.
The heat treatment process of the step (3) is that the temperature is raised to 350 ℃ and 750 ℃ at the speed of 2 ℃/min and is respectively preserved for 2 hours.
The invention has the following remarkable advantages:
(1) By adding a proper amount of BaO, the thermal property of the microcrystal sealing glass is effectively improved, particularly the thermal expansion coefficient is improved, the microcrystal sealing glass is matched with other SOFC components, and the microcrystal sealing glass plays a prominent role in the sealing property after long-term operation and thermal cycle.
(2) The addition of BaO can also obviously reduce the characteristic temperature of the glass, improve the sealing capacity between the glass and a base material, improve the softening and self-healing capacity at the working temperature and effectively avoid sealing failure.
(3) Compared with other BaO-containing glass, the sealing glass is more suitable for sealing the medium-temperature SOFC, has stable chemical properties, and does not react with other components of the SOFC after long-term operation.
(4) The raw materials selected by the invention are common and easy to obtain, the preparation process is stable and feasible, the use method is simple, and the practical and industrialized conditions are achieved.
Drawings
FIG. 1 is a graph comparing thermal expansion curves of examples 1, 2 and 3.
FIG. 2 is a graph comparing the differential thermal analysis curves of examples 1, 2 and 3.
Fig. 3 is a scanning electron microscope image and line scan energy spectrum of a polished cross section of a NiO-YSZ anode support/microcrystalline sealing glass/SUS 430 stainless steel three-layer structure after 50 hours of sealed SOFC testing using example 2.
Detailed Description
The present invention is further illustrated by the following examples, but the scope of the present invention is not limited to the following examples.
TABLE 1 Table of compositions of microcrystalline sealing glasses (mol%) in examples 1-3
The invention is further illustrated by the following examples.
Example 1:
(1) According to the mixture ratio of each component in the example 1 in the table, a certain amount of analytically pure raw materials are weighed, ground by a mortar for 1 hour and uniformly mixed; then, putting the powder into a platinum crucible, placing the platinum crucible in the air atmosphere of a box-type resistance furnace, heating to 1300 ℃ at the speed of 2 ℃/min, and preserving heat for 2 hours; then, taking out the crucible, pouring the melt into deionized water for quenching, and drying to obtain fragments of the glass melt;
(2) And grinding the glass melt fragments, and sieving the ground glass melt fragments with a 325-mesh sieve to obtain glass powder. Mixing glass powder and a binder (ethyl cellulose: terpineol = 4) in a mass ratio of 3.5.
(3) Coating a little sealant slurry on the surfaces of an SUS430 stainless steel and a NiO-YSZ anode support type SOFC, slowly heating to 150 ℃, preserving heat for 1 hour, then heating to 350 ℃ at the speed of 2 ℃/min in an electric furnace, preserving heat for 2 hours, and heating to 750 ℃ at the speed of 2 ℃/min, and carrying out heat treatment for 2 hours to complete sealing.
Example 2:
(1) Weighing a certain amount of analytically pure raw materials according to the mixture ratio of the components in the example 2 in the table, grinding the raw materials by using a mortar for 1 hour, and uniformly mixing the raw materials; then, the powder is put into a platinum crucible, placed in the air atmosphere of a box-type resistance furnace, heated to 1350 ℃ at the speed of 2 ℃/min and kept warm for 1.5 hours; then, taking out the crucible, pouring the melt into deionized water for quenching, and drying to obtain fragments of the glass melt;
(2) And grinding the glass melt fragments, and sieving the ground glass melt fragments with a 325-mesh sieve to obtain glass powder. Mixing glass powder and a binder (ethyl cellulose: terpineol =4 = 96) in a mass ratio of 3:1 to form slurry, and uniformly grinding the slurry in a mortar to obtain the sealant slurry.
(3) Coating a little sealant slurry on the surfaces of an SUS430 stainless steel and a NiO-YSZ anode support type SOFC, slowly heating to 150 ℃, preserving heat for 1.5 hours, then heating to 350 ℃ at the speed of 2 ℃/min in an electric furnace, preserving heat for 2 hours, and heating to 750 ℃ at the speed of 2 ℃/min for heat treatment for 2 hours to complete sealing.
Example 3:
(1) Weighing a certain amount of analytically pure raw materials according to the mixture ratio of the components in the example 3 in the table, grinding the raw materials by using a mortar for 1 hour, and uniformly mixing the raw materials; then, putting the powder into a platinum crucible, placing the platinum crucible in the air atmosphere of a box-type resistance furnace, heating to 1400 ℃ at the speed of 2 ℃/min, and preserving heat for 1 hour; then, taking out the crucible, pouring the melt into deionized water for quenching, and drying to obtain fragments of the glass melt;
(2) And grinding the glass melt fragments, and sieving with a 325-mesh sieve to obtain glass powder. Mixing glass powder and a binder (ethyl cellulose: terpineol = 4) in a mass ratio of 2.5 to 1 to form slurry, and uniformly grinding the slurry in a mortar to obtain the sealant slurry.
(3) Coating a little sealant slurry on the surfaces of an SUS430 stainless steel and a NiO-YSZ anode support type SOFC, slowly heating to 150 ℃, preserving heat for 2 hours, then heating to 350 ℃ at the speed of 2 ℃/min in an electric furnace, preserving heat for 2 hours, and heating to 750 ℃ at the speed of 2 ℃/min, and carrying out heat treatment for 2 hours to complete sealing.
And (3) performance characterization:
FIG. 1 is a graph comparing the thermal expansion curves of BaO-containing SOFC microcrystalline sealing glasses of examples 1-3. CTE and T were measured at 300 ℃ to 600 ℃ in air at a heating rate of 5 ℃/min using a thermal expansion instrument (DIL 402C, NETZSCH Inc.) s . Examples 1, 2 and 3 SOFC microcrystalline sealing glasses containing BaO had respective CTEs of 8.87 × 10 –6 K –1 、9.73×10 –6 K –1 And 11.07X 10 –6 K –1 (ii) a T of glass s 694 ℃, 683 ℃ and 682 ℃ respectively. Shows that the CTE of the SOFC microcrystalline sealing glass gradually increases along with the increase of the BaO content, and T s And gradually decreases. Three glass CTE match SOFC Components, T s Illustrating the ability to operate at SOFC temperatures with adjacent stacksThe part has better wettability and softening self-healing capability.
FIG. 2 is a comparative graph of the differential thermal analysis curves of the BaO-containing SOFC microcrystalline sealing glass powders of examples 1-3. By means of a synchronous thermal analyser (STA 449F, NETZSCH Inc.) in N 2 T of the glass powder was measured at a heating rate of 10 ℃/min under an atmosphere g And T c . Examples 1, 2 and 3T of BaO-containing SOFC microcrystalline sealing glass powders g 663 deg.C, 638 deg.C, 619 deg.C, respectively; t of glass c 764 deg.c, 634 deg.c and 714 deg.c, respectively. All three types of glass can complete glass transition at the SOFC working temperature, and can generate slight crystallization at the working temperature of 750 ℃ so as to enhance the strength of the glass and reduce the cracks of gas leakage.
Fig. 3 is a scanning electron microscope image and a line scan energy spectrum of a polished cross section of a NiO-YSZ anode support/microcrystalline sealing glass/SUS 430 stainless steel three-layer structure after 50 hours of testing using a NiO-YSZ anode support type SOFC sealed with a microcrystalline sealing glass containing BaO of example 2. The interface is tightly combined, and no obvious element is diffused, so that the microcrystal sealing glass has excellent air tightness under the condition of long-time operation.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (8)
1. A use method of BaO-containing microcrystal sealing glass of a solid oxide fuel cell is characterized by comprising the following steps: the microcrystalline glass is prepared from BaO, mgO and Al as raw materials 2 O 3 、B 2 O 3 And SiO 2 Prepared according to the molar ratio of (30) - (40) - (10) - (20) - (1~5) - (8) - (12) - (35) - (55), and specifically comprises the following steps:
(1) Uniformly mixing a certain amount of raw materials and then melting; quenching the melted glass liquid to obtain a glass frit; crushing, grinding or ball-milling the glass frit, and sieving to obtain glass powder;
(2) Mixing glass powder and an organic binder into slurry, and performing ball milling or grinding until the slurry is uniformly dispersed to obtain a glass sealing element raw material;
(3) Placing the glass sealing element raw material between the flat-plate solid oxide fuel cell and the stainless steel connector material, slowly heating and drying, and then carrying out heat treatment to obtain the sealing.
2. The method of claim 1, wherein: the melting process in the step (1) is carried out at 1300 to 1400 ℃ for 1~2 hours.
3. The method of claim 1, wherein: the particle size of the glass powder sieved in the step (1) is less than or equal to 45 mu m.
4. The method of claim 1, wherein: the organic binder in the step (2) is a mixture of ethyl cellulose and terpineol with the mass ratio of 4.
5. The method of claim 1, wherein: the mass ratio of the glass powder to the organic binder in the step (2) is 2.5 to 3.5.
6. The method of claim 1, wherein: the drying process in the step (3) is 100 to 150 ℃, and the temperature is kept for 1~2 hours.
7. The method of claim 1, wherein: and (4) selecting a NiO-YSZ anode-supported solid oxide fuel cell as the flat-plate solid oxide fuel cell in the step (3), and selecting SUS430 type stainless steel as a stainless steel connector material.
8. The method of claim 1, wherein: the sealing heat treatment process in the step (3) is to heat the temperature to 350 ℃ at the speed of 2 ℃/min for 2 hours, and then heat the temperature to 750 ℃ at the speed of 2 ℃/min for 2 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310011755.0A CN115959832B (en) | 2023-01-05 | BaO-containing solid oxide fuel cell microcrystalline sealing glass and preparation and use methods thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310011755.0A CN115959832B (en) | 2023-01-05 | BaO-containing solid oxide fuel cell microcrystalline sealing glass and preparation and use methods thereof |
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| Publication Number | Publication Date |
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| CN115959832A true CN115959832A (en) | 2023-04-14 |
| CN115959832B CN115959832B (en) | 2024-07-26 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20050028069A (en) * | 2003-09-17 | 2005-03-22 | 현대자동차주식회사 | Composition of sealing glass for solid oxide fuel cell |
| CN102341357A (en) * | 2009-03-04 | 2012-02-01 | 肖特公开股份有限公司 | Crystallizing glass solder and use thereof |
| CN114349349A (en) * | 2022-03-17 | 2022-04-15 | 河北省沙河玻璃技术研究院 | Medium-high temperature SOFC sealing microcrystalline glass, sealing material, preparation method and use method |
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20050028069A (en) * | 2003-09-17 | 2005-03-22 | 현대자동차주식회사 | Composition of sealing glass for solid oxide fuel cell |
| CN102341357A (en) * | 2009-03-04 | 2012-02-01 | 肖特公开股份有限公司 | Crystallizing glass solder and use thereof |
| CN114349349A (en) * | 2022-03-17 | 2022-04-15 | 河北省沙河玻璃技术研究院 | Medium-high temperature SOFC sealing microcrystalline glass, sealing material, preparation method and use method |
Non-Patent Citations (1)
| Title |
|---|
| 陈虎;吴也凡;: "IT-SOFC硼酸盐封接玻璃的相关性能研究", 陶瓷学报, no. 02, 15 June 2012 (2012-06-15), pages 1 * |
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