JP4996171B2 - 水素ガスセンサ - Google Patents
水素ガスセンサ Download PDFInfo
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- JP4996171B2 JP4996171B2 JP2006224493A JP2006224493A JP4996171B2 JP 4996171 B2 JP4996171 B2 JP 4996171B2 JP 2006224493 A JP2006224493 A JP 2006224493A JP 2006224493 A JP2006224493 A JP 2006224493A JP 4996171 B2 JP4996171 B2 JP 4996171B2
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- JP
- Japan
- Prior art keywords
- sensitive element
- hydrogen gas
- added
- acid
- gas sensor
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims description 104
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 62
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 44
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 31
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 22
- 239000004065 semiconductor Substances 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 230000004044 response Effects 0.000 claims description 5
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 239000002253 acid Substances 0.000 description 39
- 238000001514 detection method Methods 0.000 description 29
- 239000007789 gas Substances 0.000 description 29
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 26
- 230000008859 change Effects 0.000 description 22
- 230000035945 sensitivity Effects 0.000 description 18
- 238000012360 testing method Methods 0.000 description 18
- 208000005374 Poisoning Diseases 0.000 description 15
- 238000011156 evaluation Methods 0.000 description 15
- 231100000572 poisoning Toxicity 0.000 description 15
- 230000000607 poisoning effect Effects 0.000 description 15
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 14
- 239000000446 fuel Substances 0.000 description 14
- 239000000843 powder Substances 0.000 description 14
- 239000000758 substrate Substances 0.000 description 14
- 239000000203 mixture Substances 0.000 description 13
- 239000001301 oxygen Substances 0.000 description 13
- 229910052760 oxygen Inorganic materials 0.000 description 13
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 12
- 229910006404 SnO 2 Inorganic materials 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 230000001590 oxidative effect Effects 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 229910052697 platinum Inorganic materials 0.000 description 9
- 229910001260 Pt alloy Inorganic materials 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000002737 fuel gas Substances 0.000 description 7
- 238000011282 treatment Methods 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000012212 insulator Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 5
- 230000006641 stabilisation Effects 0.000 description 5
- 238000011105 stabilization Methods 0.000 description 5
- 230000036962 time dependent Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 230000004043 responsiveness Effects 0.000 description 4
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000011276 addition treatment Methods 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- -1 oxygen ions Chemical class 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
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- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Description
図1,2に示す構成の水素ガスセンサを作製した。このとき、感応素子1は次のようにして作製した。
参考例1において、上記チオ尿素の添加処理に代えて、焼結体に5%硫酸溶液を塗布した後に450℃で3分間焼成する操作を30回繰り返し行い、硫酸を添加した。それ以外は参考例1と同様にして水素ガスセンサを作製した。
参考例1において、上記チオ尿素の添加処理の後、焼結体に30%硫酸溶液を塗布した後に450℃で3分間焼成する操作を1回行い、硫酸を添加した。それ以外は参考例1と同様にして水素ガスセンサを作製した。
参考例1において、チオ尿素の添加処理を行わなかった。それ以外は参考例1と同様にして水素ガスセンサを作製した。
参考例1〜2,実施例3及び比較例1で得られた水素ガスセンサについて、感応素子1を450℃に加熱した状態で感応素子1を空気雰囲気中に曝露し、この状態で感応素子1の電気抵抗値(Rair)を測定した。
参考例1〜2及び比較例1について、検知感度が経時的に安定した状態の感応素子1に、感応素子1に硫酸5%水溶液を1回塗布し、450℃で3分間焼成した。次いで、処理後の感応素子1を用い、上記の場合と同様にして水素ガスを含む雰囲気中に曝露し、素子温度450℃での、雰囲気中の水素ガスの濃度変化に対する感応素子1の電気抵抗値(R)の変化を調査した。
参考例1について、約3分ごとに感応素子1の周囲への水素ガスの注入と感応素子1の周囲からの水素を含むガスの排気とを交互に行うことにより、感応素子1の周囲の雰囲気を空気雰囲気と、水素ガスを5000ppm含む雰囲気とに、交互に置換した。この場合の、感応素子1の電気抵抗値Rの経時変化を調査した。
参考例1及び実施例3について、感応素子1を通電して450℃に加熱した状態で放置した場合の、空気雰囲気下での電気抵抗値Rairと水素ガス雰囲気下(濃度1000ppm)での電気抵抗値Rの測定結果の変化を調査した。
Claims (3)
- 水素に感応して電気抵抗値の変化を生じる酸化物半導体を含有する感応素子を備え、前記感応素子には、硫酸及びチオ尿素が添加されていることを特徴とする水素ガスセンサ。
- 上記感応素子にアルミナゾルが添加されていることを特徴とする請求項1に記載の水素ガスセンサ。
- 上記感応素子が、チオ尿素が添加された後、硫酸が添加されているものであることを特徴とする請求項1又は2に記載の水素ガスセンサ。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2006224493A JP4996171B2 (ja) | 2006-08-21 | 2006-08-21 | 水素ガスセンサ |
Applications Claiming Priority (1)
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---|---|---|---|
JP2006224493A JP4996171B2 (ja) | 2006-08-21 | 2006-08-21 | 水素ガスセンサ |
Publications (3)
Publication Number | Publication Date |
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JP2008046091A JP2008046091A (ja) | 2008-02-28 |
JP2008046091A5 JP2008046091A5 (ja) | 2009-10-01 |
JP4996171B2 true JP4996171B2 (ja) | 2012-08-08 |
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JP2006224493A Active JP4996171B2 (ja) | 2006-08-21 | 2006-08-21 | 水素ガスセンサ |
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Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6526587B2 (ja) * | 2016-03-10 | 2019-06-05 | 株式会社東芝 | 水素センサシステム |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61117443A (ja) * | 1984-11-14 | 1986-06-04 | Mitsui Toatsu Chem Inc | ガス状水素化物の検知方法 |
JPS62261947A (ja) * | 1986-05-08 | 1987-11-14 | Figaro Eng Inc | 自己発熱型ガスセンサの製造方法 |
JPS62261948A (ja) * | 1986-05-08 | 1987-11-14 | Figaro Eng Inc | 自己発熱型ガスセンサの製造方法 |
JPH06196188A (ja) * | 1992-12-24 | 1994-07-15 | Hitachi Ltd | 燃料電池水素供給システム |
JP3795944B2 (ja) * | 1995-12-18 | 2006-07-12 | エフアイエス株式会社 | 半導体式ガスセンサの製造方法 |
JP2000074866A (ja) * | 1998-06-16 | 2000-03-14 | Figaro Eng Inc | Coセンサおよびその製造方法 |
JP2002071611A (ja) * | 2000-08-30 | 2002-03-12 | Fis Kk | 水素ガスセンサ |
JP4376093B2 (ja) * | 2003-11-12 | 2009-12-02 | 富士電機機器制御株式会社 | 薄膜ガスセンサ |
WO2006011202A1 (ja) * | 2004-07-28 | 2006-02-02 | Fis Inc. | 半導体ガスセンサ |
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2006
- 2006-08-21 JP JP2006224493A patent/JP4996171B2/ja active Active
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