JPS6345552A - Gaseous carbon monoxide sensor - Google Patents
Gaseous carbon monoxide sensorInfo
- Publication number
- JPS6345552A JPS6345552A JP19021386A JP19021386A JPS6345552A JP S6345552 A JPS6345552 A JP S6345552A JP 19021386 A JP19021386 A JP 19021386A JP 19021386 A JP19021386 A JP 19021386A JP S6345552 A JPS6345552 A JP S6345552A
- Authority
- JP
- Japan
- Prior art keywords
- oxide
- tin oxide
- alkaline earth
- mol
- sensitivity
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims description 11
- 229910002091 carbon monoxide Inorganic materials 0.000 title claims description 10
- 229910001887 tin oxide Inorganic materials 0.000 claims abstract description 37
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 36
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 23
- 239000004065 semiconductor Substances 0.000 claims abstract description 23
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 22
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 35
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 16
- 229910052791 calcium Inorganic materials 0.000 claims description 16
- 239000011575 calcium Substances 0.000 claims description 16
- 229910052788 barium Inorganic materials 0.000 claims description 10
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052790 beryllium Inorganic materials 0.000 claims description 10
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052712 strontium Inorganic materials 0.000 claims description 10
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 10
- 150000001340 alkali metals Chemical class 0.000 claims description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- 229910052701 rubidium Inorganic materials 0.000 claims description 6
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 229960004643 cupric oxide Drugs 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 230000035945 sensitivity Effects 0.000 abstract description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 16
- 229910000272 alkali metal oxide Inorganic materials 0.000 abstract description 10
- 239000000843 powder Substances 0.000 abstract description 7
- -1 alkaline earth metal salt Chemical class 0.000 abstract description 4
- 238000001035 drying Methods 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000010419 fine particle Substances 0.000 abstract description 2
- 229910000510 noble metal Inorganic materials 0.000 abstract description 2
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 238000000151 deposition Methods 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 38
- 238000000034 method Methods 0.000 description 14
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 10
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 238000001514 detection method Methods 0.000 description 7
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 229910006853 SnOz Inorganic materials 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- FRWYFWZENXDZMU-UHFFFAOYSA-N 2-iodoquinoline Chemical compound C1=CC=CC2=NC(I)=CC=C21 FRWYFWZENXDZMU-UHFFFAOYSA-N 0.000 description 1
- KOAWAWHSMVKCON-UHFFFAOYSA-N 6-[difluoro-(6-pyridin-4-yl-[1,2,4]triazolo[4,3-b]pyridazin-3-yl)methyl]quinoline Chemical compound C=1C=C2N=CC=CC2=CC=1C(F)(F)C(N1N=2)=NN=C1C=CC=2C1=CC=NC=C1 KOAWAWHSMVKCON-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 101100365756 Omphalotus olearius omo1 gene Proteins 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 1
- KOPBYBDAPCDYFK-UHFFFAOYSA-N caesium oxide Chemical compound [O-2].[Cs+].[Cs+] KOPBYBDAPCDYFK-UHFFFAOYSA-N 0.000 description 1
- 229910001942 caesium oxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- UFQXGXDIJMBKTC-UHFFFAOYSA-N oxostrontium Chemical compound [Sr]=O UFQXGXDIJMBKTC-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910001952 rubidium oxide Inorganic materials 0.000 description 1
- CWBWCLMMHLCMAM-UHFFFAOYSA-M rubidium(1+);hydroxide Chemical compound [OH-].[Rb+].[Rb+] CWBWCLMMHLCMAM-UHFFFAOYSA-M 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- CVNKFOIOZXAFBO-UHFFFAOYSA-J tin(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Sn+4] CVNKFOIOZXAFBO-UHFFFAOYSA-J 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
Landscapes
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
この発明は各種燃焼器具、溶鉱炉などから発生、あるい
は各種化学工場等で発生する一酸化炭素ガスを検知する
ためのガスセンサに関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a gas sensor for detecting carbon monoxide gas generated from various combustion appliances, blast furnaces, etc., or generated at various chemical factories.
一酸化炭素（以下ＣＯと記す）を検知するべく開発され
ているガスセンサとしては（１）湿式の定電位電解方式
のもの、（２）半導体式（主として酸化スズの焼結体）
、（３）接触燃焼方式のもの、及び（４）酸素イオン伝
導性固体電解質を利用したもの、がある。これらのＣＯ
検知原理は、それぞれ異なり次の如くである。即ち（１
）の方式は反応極でＣＯがＣＯ□に酸化され対極でＯｔ
がＨｚＯに還元されるときに生じる電流をキャッチする
。Gas sensors that have been developed to detect carbon monoxide (hereinafter referred to as CO) include (1) wet constant potential electrolysis type, and (2) semiconductor type (mainly a sintered body of tin oxide).
, (3) those using a catalytic combustion method, and (4) those using an oxygen ion conductive solid electrolyte. These CO
The detection principles are different and are as follows. That is, (1
) method, CO is oxidized to CO□ at the reaction electrode and Ot at the counter electrode.
Catch the current generated when is reduced to HzO.
（２）の方式はＣＯを吸着したときの半導体の導電性の
変化をとらえ、（３）の方式ではＣＯを触媒で燃焼させ
るときの温度変化を白金電極の抵抗値変化としてとらえ
るものである。又、（４）の方式はジルコニアチップの
一側面にＣＯ不燃焼多孔層を配し他側面にＣＯ燃焼性多
孔層を配してあり、ＣＯ燃焼の際に上記−側から他側へ
酸素イオンが伝導することを電気信号として取出すもの
である。Method (2) captures the change in conductivity of the semiconductor when CO is adsorbed, and method (3) captures the temperature change when CO is combusted by a catalyst as a change in the resistance value of the platinum electrode. In addition, in the method (4), a CO non-combustible porous layer is arranged on one side of the zirconia chip and a CO combustible porous layer is arranged on the other side, and when CO is burned, oxygen ions are transferred from the negative side to the other side. The conduction is extracted as an electrical signal.
しかし、それらの従来公知のセンサにはそれぞれ欠点が
ある。（１）のものは長期間使用中に電解液の濃度変化
（水分蒸発などによる）を生じるから液の更新などのメ
ンテナンスを必要とし、（２）のものでは水素に対する
感度よりもＣＯ感度を高め、いわゆるＣＯ選択性を得る
べく動作温度を低く （例えば１００℃以下）するので
空気中の水分、油脂分を自動的に蒸発ないし分解させる
ことができず、従って定期的な高温パージ操作を必要と
する。（３）のものは間接的な検知方式のゆえに高感度
を実現できず、（４）のものでは構造が複雑で大型であ
るから動作温度維持のための消費電力が大となるほか、
量産には適していない。However, each of these previously known sensors has drawbacks. Type (1) requires maintenance such as updating the electrolyte because the concentration of the electrolyte changes (due to water evaporation, etc.) during long-term use, and type (2) has higher CO sensitivity than hydrogen sensitivity. In order to obtain so-called CO selectivity, the operating temperature is kept low (for example, below 100°C), so moisture and oil in the air cannot be automatically evaporated or decomposed, and therefore periodic high-temperature purge operations are required. do. The method (3) cannot achieve high sensitivity because it uses an indirect detection method, and the method (4) has a complicated structure and is large, so it consumes a lot of power to maintain the operating temperature.
Not suitable for mass production.
本発明は上記（１）〜（４）のタイプのうち、（２）の
タイプ即ち酸化スズの焼結体を用いた半導体式のＣＯガ
スセンサを改良しようとするものであり、具体的には前
述の１００℃よりももかに高温の約３００〜３５０℃以
上、場合によっては約４５０℃前後で動作させることで
前述の欠点を解消しつつ、しかも優れたＣＯ選択性を発
揮するＣＯガスセンサを提供しようとするものである。The present invention aims to improve the type (2) of the types (1) to (4) above, that is, the semiconductor type CO gas sensor using a sintered body of tin oxide. The present invention aims to provide a CO gas sensor that eliminates the above-mentioned drawbacks and exhibits excellent CO selectivity by operating at a temperature of about 300 to 350°C or higher, in some cases around 450°C, which is much higher than the 100°C of 100°C. It is something to do.
本発明者はこの技術課題を解決するべく種々研究の結果
、酸化スズ半導体にアルカリ土類金属を添加すれば高温
動作時のＣＯ選択性が顕著に改良されるという知見を得
た。本発明はこの知見に基づいて完成されたものである
。As a result of various studies aimed at solving this technical problem, the inventors of the present invention have found that adding an alkaline earth metal to a tin oxide semiconductor significantly improves CO selectivity during high-temperature operation. The present invention was completed based on this knowledge.
即ち、本第１発明に係るＣＯガスセンサの特徴構成は、
酸化スズ半導体に、ベリリウム、カルシウム、ストロン
チウム及びバリウムの中から選ばれた少なくとも１種の
アルカリ土類金属の酸化物が、１．０ｍｏｌ％以上添加
されている点にあり、また第２発明の特徴構成は、酸化
スズ半導体に、ベリリウム、カルシウム、ストロンチウ
ム及びバリウムの中から選ばれた少なくとも１種のアル
カリ土類金属の酸化物が１．０ｍｏｌ％以上と、ナトリ
ウム、カリウム、ルビジウム及びカルシウムの中から選
ばれた少なくとも１種のアルカリ金属の酸化物が０．５
ｍｏｌ％以上とが、それぞれ添加されている点にあり、
さらに第３発明の特徴構成は酸化スズ半導体に、ベリリ
ウム、カルシウム、ストロンチウム及びバリウムの中か
ら選ばれた少なくとも１種のアルカリ土類金属の酸化物
が１．０ｍｏｌ％以上と、酸化第二銅が０．０５〜１．
ｏｍｏ１％とが、それぞれ添加されていること点にあり
、また第４発明の特徴構成は、酸化スズ半導体に、ベリ
リウム、カルシウム、ストロンチウム及びバリウムの中
から選ばれた少なくとも１種のアルカリ土類金属の酸化
物が１゜０ｍ０１％以上と、ナトリウム、カリウム、ル
ビジウム及びカルシウムの中から選ばれた少なくとも１
種のアルカリ金属の酸化物が０．５ｍｏｌ％以上と、酸
化第二銅が０．０５〜１ 、０ｎｔｏ １％とが、それ
ぞれ添加されている点にある。That is, the characteristic configuration of the CO gas sensor according to the first invention is as follows:
A feature of the second invention is that 1.0 mol% or more of an oxide of at least one alkaline earth metal selected from beryllium, calcium, strontium, and barium is added to the tin oxide semiconductor. The composition includes a tin oxide semiconductor containing 1.0 mol% or more of an oxide of at least one alkaline earth metal selected from beryllium, calcium, strontium, and barium, and at least 1.0 mol% of an oxide selected from among sodium, potassium, rubidium, and calcium. The oxide of at least one selected alkali metal is 0.5
The point is that mol% or more is added, respectively.
Furthermore, the characteristic structure of the third invention is that 1.0 mol% or more of an oxide of at least one alkaline earth metal selected from beryllium, calcium, strontium, and barium is added to the tin oxide semiconductor, and cupric oxide is added to the tin oxide semiconductor. 0.05-1.
omo1%, respectively, and the characteristic configuration of the fourth invention is that at least one alkaline earth metal selected from beryllium, calcium, strontium, and barium is added to the tin oxide semiconductor. oxide of 1°0m01% or more, and at least one selected from sodium, potassium, rubidium, and calcium.
The point is that 0.5 mol % or more of the seed alkali metal oxide and 0.05 to 1% and 0nto 1% of cupric oxide are added, respectively.
前記アルカリ土類金属のうちマグネシウムは他の同族元
素とやや挙動を異にし、ＣＯ選択性の向上の効果が比較
的小であるから好適実施例から除外される。また、酸化
スズ（ＳｎＯｚ）に対するアルカリ土類金属酸化物の添
加量が１ 、０ｍｏ １％未満では上記効果が不十分と
なるので好ましくない。Among the alkaline earth metals, magnesium behaves somewhat differently from other homologous elements, and the effect of improving CO selectivity is relatively small, so it is excluded from the preferred embodiments. Further, if the amount of alkaline earth metal oxide added to tin oxide (SnOz) is less than 1.0 mo 1%, the above effects will be insufficient, which is not preferable.
また、第２発明においては、アルカリ土類金属の酸化物
とアルカリ金属の酸化物とを併用して酸化スズ（Ｓｎｏ
ｔ）に添加するものであるが、アルカリ金属の酸化物の
酸化スズ（ＳｎＯｚ）に対する添加量がＱ、Ｓｎｏｔ％
未満では上記効果が不十分となるのでやはり好ましくな
い。Further, in the second invention, an alkaline earth metal oxide and an alkali metal oxide are used together to form tin oxide (Sno
t), the amount of alkali metal oxide added to tin oxide (SnOz) is Q, Snot%
If it is less than that, the above effects will be insufficient, so it is still not preferable.
さらに、第３発明及び第４発明においては、酸化第二！
＊（ＣｕＯ）をさらに添加するものであるが、酸化第二
Ｍｉ４（Ｃｕｂ）の酸化スズに対する添加量が０．Ｓｎ
ｏｔ％未満の場合には添加効果が少ないものである。Furthermore, in the third and fourth inventions, oxidized second!
*(CuO) is further added, but the amount of secondary Mi4 (Cub) oxide added to tin oxide is 0. Sn
If it is less than ot%, the effect of addition is small.
上記において「添加」のための方法としては下記の含浸
法、混合法等の中から適宜選択すればよい。ここに含浸
法とは酸化スズの焼結体を上記アルカリ土類金属の可溶
性化合物の溶液の中へ浸漬し、含浸された該化合物を分
解して酸化物とする方法を意味し、混合法とはスズ及び
アルカリ土類金属の水酸化物をよく混合したのちに焼結
する方法を意味する。In the above, the method for "adding" may be appropriately selected from among the following impregnation methods, mixing methods, etc. The impregnation method here refers to a method in which a sintered body of tin oxide is immersed in a solution of the above-mentioned soluble compound of alkaline earth metal, and the impregnated compound is decomposed into an oxide. means a method in which tin and alkaline earth metal hydroxide are thoroughly mixed and then sintered.
つまり、第１発明においては、酸化スズ（Ｓｎｕｇ）に
アルカリ土類金属の少なくとも一つを含む金属の酸化物
を担持させることによって、酸化スズの表面を塩基的に
改質させ、ＣＯガスを酸化スズ（ＳｎＯ□）半導体に選
択的に作用させることができる。That is, in the first invention, by making tin oxide (Snug) carry a metal oxide containing at least one alkaline earth metal, the surface of the tin oxide is basicly modified, and CO gas is oxidized. It can act selectively on tin (SnO□) semiconductors.
また、第２発明にあっては、上記作用に加えアルカリ土
類金属の酸化物とアルカリ金属の酸化物とを併用して添
加することにより、前記アルカリ土類の酸化物のみの場
合に比べて少量の添加量でＣＯガスを酸化スズ半導体に
選択的に作用させることかできる。すなわち、共存ガス
としてのＨ２やＣｚ）ｌｓｏｌ（（エタノール）は例え
ばＮａ、０、Ｋ２Ｏと反応して金属水酸化物あるいはア
ルコラードを形成する傾向にあるから、少なくともこれ
らは金属酸化物に捕捉され、従って酸化スズの電導度に
影響を与え難くなるのではないかと推測される。In addition, in the second invention, in addition to the above effects, by adding an alkaline earth metal oxide and an alkali metal oxide in combination, compared to the case of using only the alkaline earth metal oxide, By adding a small amount of CO gas, it is possible to selectively act on the tin oxide semiconductor. That is, since H2 and Cz)lsol((ethanol) as coexisting gases tend to react with, for example, Na, 0, and K2O to form metal hydroxides or alcoholades, at least these are captured by metal oxides, Therefore, it is presumed that tin oxide is less likely to affect the electrical conductivity.
さらに、第３発明では、前記第１発明及び第２発明の作
用に加え、アルカリ土類金属の酸化物に対しＣｕＯを０
．００５〜１ ｍｏ１％添加し、又はアルカリ土類金属
及びアルカリ金属酸化物の併用系でＣｕＯを０．００５
〜１ ｍｏ１％添加することにより、アルコール感度を
低（おえることができる。Furthermore, in the third invention, in addition to the effects of the first and second inventions, CuO is added to the alkaline earth metal oxide.
．． 0.005 to 1 mo1%, or a combination system of alkaline earth metal and alkali metal oxide with CuO of 0.005
By adding ~1 mo1%, alcohol sensitivity can be lowered.
この発明のＣＯガスセンサは既述の如く冒記の（２）の
タイプに属することから構造が簡単で小型であり、消費
電力が少なく量産に通し、メンテナンスフリーである等
の長所を備えていることに加え、本発明による独特の効
果は少量の添加で優れたＣＯ／Ｈ！選択性及び高いＣＯ
感度特性が得られ、またアルコール感度をおさえた状態
で優れたＣＯ選択性を示す点と、高温動作において優れ
たＣＯ選択性を示し、さらに従来低温動作時に必要であ
った周期的な高温パージ操作が不要化された点である。As mentioned above, the CO gas sensor of the present invention belongs to the type (2) mentioned above, so it has advantages such as simple and small structure, low power consumption, suitable for mass production, and maintenance-free. In addition to this, the unique effect of the present invention is that even a small amount of CO/H can be added! Selectivity and high CO
It has excellent sensitivity characteristics, exhibits excellent CO selectivity with suppressed alcohol sensitivity, and exhibits excellent CO selectivity in high temperature operation, as well as periodic high temperature purge operations that were conventionally required during low temperature operation. is no longer necessary.
Ａ、ガスセンサの作成
前述の含浸法の場合について本発明のガスセンサの製法
を先ず説明すると、出発物質としては市販の四塩化スズ
（ＳｎＣ１ｎ）を用い、一定濃度の水溶液を調製する。A. Preparation of Gas Sensor Firstly, the method for producing the gas sensor of the present invention will be explained using the impregnation method described above. Commercially available tin tetrachloride (SnC1n) is used as a starting material, and an aqueous solution of a certain concentration is prepared.
この水溶液にアンモニア水を滴下して得た水酸化スズの
沈殿物を乾燥後電気炉で焼成して半導性の酸化スズを得
る。これを粉砕して微粉末とし水で練ってペースト状と
し、このペーストを第１図の如くガスセンサの検出電極
としての貴金属コイル（１）へ約０．５ｆｌの直径の球
体（２）となるよう付着させる。この球体が後記の半導
体部（６）となるものである。乾燥後、貴金属コイル（
１）へ所定の電流を通して加熱し、所定の温度、例えば
約８００℃で酸化スズの粉末を焼結させる。焼結により
外観形状は変わることなく第１図のままであるが、微視
的には多孔状となっている。The tin hydroxide precipitate obtained by dropping ammonia water into this aqueous solution is dried and then fired in an electric furnace to obtain semiconductive tin oxide. This is crushed into a fine powder, kneaded with water to form a paste, and this paste is applied to the noble metal coil (1) as the detection electrode of the gas sensor to form a sphere (2) with a diameter of about 0.5 fl as shown in Figure 1. Make it adhere. This sphere becomes a semiconductor section (6) to be described later. After drying, the precious metal coil (
1) Heat the tin oxide powder by passing a predetermined current through it to sinter the tin oxide powder at a predetermined temperature, for example, about 800°C. Although the external shape remains unchanged as shown in Fig. 1 due to sintering, microscopically it has become porous.
一方、アルカリ土類金属の水溶性の塩、例えば硝酸塩、
酢酸塩の水溶液を準備しであるので、この溶液の中へ前
記多孔性の酸化スズ焼結体を浸し、乾燥後に再度通電す
ることで約６００℃とし、上記硝酸塩又は酢酸塩を熱分
解する。これにより硝酸基、酢酸基は分解揮散してアル
カリ土類金属は酸化物となり、その微粒（３）は第２図
の如く酸化スズの粉（４）の表面に担持された状態の、
ガスセンサ（５）の半導体部（６）となる。尚、第２図
は第１図の円（Ａ）で囲まれた部分を拡大したものであ
る。On the other hand, water-soluble salts of alkaline earth metals, such as nitrates,
Since an aqueous solution of acetate is prepared, the porous tin oxide sintered body is immersed in this solution, and after drying, electricity is applied again to bring the temperature to about 600° C. to thermally decompose the nitrate or acetate. As a result, the nitrate and acetate groups are decomposed and volatilized, and the alkaline earth metal becomes an oxide, whose fine particles (3) are supported on the surface of the tin oxide powder (4) as shown in Figure 2.
This becomes the semiconductor part (6) of the gas sensor (5). Note that FIG. 2 is an enlarged view of the area surrounded by the circle (A) in FIG. 1.
Ｂ、 Ｃｏ／Ｈ，感度比の測定結果
上記のようにして作成したガスセンサ（５）は通常第３
図のようなホイーストストン回路に組込まれて用いられ
る。番号（７）はガスセンサのための負荷抵抗としてこ
れに直列に接続された抵抗であり、番号（８） 、 （
９）はこの回路の基準電位を定めるべく互いに直列に接
続された抵抗である。ガスセンサ（５）と抵抗（７）は
他の抵抗（８） 、 （９）に対し電源（１０）に関し
並列であり、各々の中間の点（１１） 、 （１２）の
あいだの不平衡電位差が出力電圧（ｍＶ）としてボルト
メータ（１３）により検知される。B. Measurement results of Co/H and sensitivity ratio The gas sensor (5) prepared as above is usually
It is used by being incorporated into the Wheatstone circuit as shown in the figure. Number (7) is a resistor connected in series with this as a load resistor for the gas sensor, and numbers (8), (
9) are resistors connected in series with each other to determine the reference potential of this circuit. The gas sensor (5) and the resistor (7) are in parallel with the other resistors (8), (9) with respect to the power supply (10), and the unbalanced potential difference between their respective midpoints (11), (12) is The output voltage (mV) is detected by a voltmeter (13).
清浄空気中での出力電圧（Ｖａ）を、ガス存在下での出
力電圧（Ｖｇ）から差引いた値が、以下感度（ΔＶ）と
して表示される。The value obtained by subtracting the output voltage (Va) in clean air from the output voltage (Vg) in the presence of gas is hereinafter displayed as sensitivity (ΔV).
ΔＶ ＝ Ｖｇ −Ｖａ
そしてΔＶ （ＣＯ）を−酸化炭素検知感度とし、ΔＶ
（Ｈりを水素ガス検知感度と定義すると、Ｃｏ／Ｈｚ感
度比は
ΔＶ （Ｃｏ）
ΔＶ（１１り
で表される。以下の試験ではＣＯガスは１１００ｐｐと
し、水素ガスはその１０倍の１１０００ｐｐとしである
から、上記感度比が１であってもＣＯガス感度はＩｔ感
度の１０倍であることを意味する。ΔV = Vg −Va And ΔV (CO) is −carbon oxide detection sensitivity, ΔV
(If H is defined as the hydrogen gas detection sensitivity, the Co/Hz sensitivity ratio is expressed as ΔV (Co) ΔV (11). In the following tests, CO gas is set to 1100 pp, and hydrogen gas is set to 11000 pp, which is 10 times that. Therefore, even if the sensitivity ratio is 1, it means that the CO gas sensitivity is 10 times the It sensitivity.
ＣＯ選択性として実用上十分であると認められるレベル
は上記感度比が約０．５以上、つまりＣＯ感度がＨ２感
度の約５倍以上のときである。The level of CO selectivity that is recognized as practically sufficient is when the sensitivity ratio is about 0.5 or more, that is, when the CO sensitivity is about 5 times or more than the H2 sensitivity.
下記第１表乃至第４表は酸化カルシウム（Ｃａｂ）、酸
化ストロンチウム（ＳｒＯ）、酸化バリウム（Ｂａｄ）
及び酸化ベリリウム（Ｂｅｄ）の添加量を替えた数種の
サンプルについて、各動作温す。なお、酸化カルシウム
添加サンプルの動作温度は４５０℃、酸化ストロンチウ
ム添加サンプルの動作温度は４３０℃、酸化バリウム添
加サンプルの動作温度は３９０℃、酸化ベリリウム添加
サンプルの動作温度は３５０℃とした。Tables 1 to 4 below show calcium oxide (Cab), strontium oxide (SrO), barium oxide (Bad)
Various operating temperatures were measured for several samples with different amounts of beryllium oxide (Bed) added. The operating temperature of the calcium oxide-added sample was 450°C, the strontium oxide-added sample was 430°C, the barium oxide-added sample was 390°C, and the beryllium oxide-added sample was 350°C.
第 １ 表
第２表
第 ３ 表
第４表
次に、第５表に各アルカリ土類金属酸化物を添加したサ
ンプルのセンサ作動温度と、感度比の結果を示す。Table 1 Table 2 Table 3 Table 4 Next, Table 5 shows the sensor operating temperatures and sensitivity ratios of samples to which each alkaline earth metal oxide was added.
第５表
以上第２〜５表から明らかな如く、アルカリ土類金属の
添加は酸化スズに対し１ 、０ｍｏ １％以上でＣＯ選
択性が良好、４．０ｍｏｌ％以上でさらに一層良好であ
り、ＣＯ濃度の変化に対しかなりの定量性があることが
確認された。As is clear from Tables 2 to 5, the CO selectivity is good when the alkaline earth metal is added to tin oxide at 1% or more, and even better when it is 4.0mol% or more. It was confirmed that there is considerable quantitative property for changes in CO concentration.
次ニｃｏカスｔａ度を１１００ｐｐと２００ｐｐｍ（７
） ２水準にとり、前記ホイーストストンブリッジの印
加電圧（つまり電源（１０）の電圧）を変えることでＢ
ａＯ６，５ｍｏｌ％添加のガスセンサの動作温度を３９
０℃から４５０℃の範囲で変更した場合のグラフを第４
図に示す。但し、縦軸には感度比ではなく感度ΔＶ （
Ｃｏ）又はΔＶ（ＯＸ）を＋ｗＶ単位でとっである。Next, the coke temperature was 1100pp and 200ppm (7
) 2 levels and by changing the voltage applied to the wheast stone bridge (that is, the voltage of the power supply (10)), B
The operating temperature of the gas sensor with 5 mol% aO6 added is 39
The graph when changing from 0℃ to 450℃ is shown in the fourth graph.
As shown in the figure. However, the vertical axis shows the sensitivity ΔV (
Co) or ΔV(OX) in units of +wV.
また、第５図にはＢａ８６．５ｍｏｌ％添加のガスセン
サの、センサ温度３９０℃における一酸化炭素ガスと、
水素ガスのガス濃度依存性を示したもので、このグラフ
から一酸化炭素ガスに対して高感度であるとともに、水
素ガスとの分離も良いことがわかる。In addition, Fig. 5 shows carbon monoxide gas at a sensor temperature of 390°C for a gas sensor containing 86.5 mol% of Ba.
This graph shows the gas concentration dependence of hydrogen gas, and it can be seen from this graph that it is highly sensitive to carbon monoxide gas and can be separated well from hydrogen gas.
また、第６図はＢａＯ添加ガスセンサの一酸化炭素ガス
と水素ガスに対する時間応答曲線を示したもので、低濃
度から高濃度に亘って（１１００ｐｐ 〜３００ｐｐｍ
）応答が早いことがわかり、また、回復も同程度に早い
ことがわかる。Figure 6 shows the time response curves of the BaO-added gas sensor for carbon monoxide gas and hydrogen gas, ranging from low to high concentrations (1100pp to 300ppm).
) It can be seen that the response is fast, and the recovery is also found to be equally fast.
９０％応答は３０秒以内に充分入り、実用上非常に望ま
しい特性を有しているものである。この場合のセンサ温
度は３９０℃、電源電圧は１．９ｖである。A 90% response is achieved within 30 seconds, which is a characteristic that is highly desirable in practice. In this case, the sensor temperature is 390° C. and the power supply voltage is 1.9V.
〔別実施例１〕
ナトリウム、カリウム、ルビジウム及びカルシウム等の
アルカリ金属の酸化物の方が、前記アルカリ土類の酸化
物に比べて少量の添加量で優れたＣＯ／Ｈ，選択性が得
られ、またＣＯ感度もアルカリ金属の方がアルカリ土類
金属に比べて２倍から３倍高いという特性を有している
ことから、酸化スズ半導体に、ベリリウム、カルシウム
、ストロンチウム及びバリウムの中から選ばれた少なく
とも１種のアルカリ土類金属の酸化物が１．０ｍｏｌ％
以上と、ナトリウム、カリウム、ルビジウム及びカルシ
ウムの中から選ばれた少なくとも１種のアルカリ金属の
酸化物がＱ 、 ５ｍｏ １％以上とをそれぞれ添加す
るようにしても良い。[Another Example 1] Oxides of alkali metals such as sodium, potassium, rubidium, and calcium can provide superior CO/H selectivity with a smaller amount added than the oxides of alkaline earth metals. In addition, since alkali metals have a property that CO sensitivity is two to three times higher than that of alkaline earth metals, tin oxide semiconductors are selected from beryllium, calcium, strontium, and barium. 1.0 mol% of at least one alkaline earth metal oxide
In addition to the above, 1% or more of an oxide of at least one alkali metal selected from sodium, potassium, rubidium, and calcium may be added.
第７図は、酸化バリウムが２．６ｍｏ１％と、アルカリ
金属の１種である酸化セシウムが２ｍｏ１％添加された
ガスセンサを用い、また、第８図は酸化バリウムが２．
６ｍｏ１％と酸化ルビジウム（ＲｂｚＯ）が２ｍｏ１％
添加されたガスセンサを用いてガスセンサの動作温度と
感度を示したグラフである。Figure 7 shows a gas sensor in which 2.6 mo1% of barium oxide and 2 mo1% of cesium oxide, which is an alkali metal, is added, and in Figure 8, 2.6 mo1% of barium oxide is added.
6mo1% and rubidium oxide (RbzO) 2mo1%
3 is a graph showing the operating temperature and sensitivity of a gas sensor using an added gas sensor.
前記グラフは第５図に示した酸化バリウムのみを添加し
たガスセンサに比べてＣｏ／Ｈｚ選択性とＣＯ感度が共
に優れていることがわかる。The graph shows that both the Co/Hz selectivity and the CO sensitivity are superior to the gas sensor shown in FIG. 5 in which only barium oxide is added.
〔別実施例２〕
さらに、前記アルカリ土類金属に対し、あるいはアルカ
リ金属及びアルカリ土類金属の併用系に対し、酸化第二
銅（Ｃｕｂ）を添加したものを、酸化スズに添加しても
良い。[Another Example 2] Furthermore, cupric oxide (Cub) may be added to tin oxide to the alkaline earth metal or to the combination system of alkali metal and alkaline earth metal. good.
すなわち、前記実施的で作成したＢａ０（６，５ｍｏｌ
％）を添加したガスセンサに対し、さらに、所定の濃度
（０，０１２ｍｏｌ／ ｌ 、 ０．０４８ｍｏｌ／
ｌ 。That is, Ba0 (6.5 mol
%), a predetermined concentration (0,012 mol/l, 0.048 mol/l) was added to the gas sensor.
l.
０．０９６ｍｏｌ／ ｌ 、０．１２ｍｏｌ／ ｌ 、
０．２ｍｏｌム０の硝酸銅溶液を、それぞれ１回づつ含
浸させ、空気中で乾燥後、コイルに電流を流して温度を
上げ焼成する、焼成条件は５００℃で１時間である。そ
の結果を第６表に示す。ＣｕＯ無添加の場合では、エタ
ノールはＣＯに対し１０倍近い感度を有するが、Ｑ、４
ｍｏ１％程度のＣｕＯ添加によりＣＯ感度よりも低くお
さえる事ができる。0.096 mol/l, 0.12 mol/l,
Each coil was impregnated once with a 0.2 mol copper nitrate solution, dried in air, and fired by passing an electric current through the coil to raise the temperature. The firing conditions were 500° C. for 1 hour. The results are shown in Table 6. In the case of no CuO addition, ethanol is nearly 10 times more sensitive to CO, but Q,4
By adding about 1% mo of CuO, the sensitivity can be kept lower than the CO sensitivity.
第６表
また、ＳｒＯとＣｕＯとを併用して酸化スズ半導体に添
加したＣＯガスに対するエタノール感度結果を第７表に
、ＣａＯとＣｕＯとを併用して酸化スズ半導体に添加し
たＣＯガスに対するエタノールの感度結果を第８表にそ
れぞれ示す。Table 6 Table 7 shows the ethanol sensitivity results for CO gas added to a tin oxide semiconductor using a combination of SrO and CuO. The sensitivity results are shown in Table 8.
第７表
ＳｒＯ（８ｍｏ１％）添加の場合センサ温度４３０℃第
８表
ＣａＯ（８ｍｏ１％）添加の場合センサ温度４５０℃前
記第７表及び第８表の結果より、ＣｕＯの添加によりエ
タノールの感度が低下することがわかり、またＳｒＯと
ＣｕＯの場合はＢａＯに比べ少し高温での動作のため、
もともとアルコール感度が低いのでＣｕＯの添加は少な
くてすむことがわかる。Table 7: When SrO (8 mo1%) is added, the sensor temperature is 430°C. Table 8: When CaO (8 mo1%) is added, the sensor temperature is 450°C. From the results in Tables 7 and 8 above, the sensitivity of ethanol is increased by the addition of CuO. In addition, since SrO and CuO operate at slightly higher temperatures than BaO,
It can be seen that since the alcohol sensitivity is originally low, the addition of CuO can be reduced.
また、このようにして得られたＣＯ検知用ガスセンサの
感度曲線を第９図に示す。第９図のグラフに見られる如
り、ＣＯとＨ２及び都市ガス（天然ガス）の主成分であ
るＣＨ４との分離は良い。Moreover, the sensitivity curve of the CO detection gas sensor obtained in this way is shown in FIG. As seen in the graph of FIG. 9, CO is well separated from H2 and CH4, which is the main component of city gas (natural gas).
また、ＬＰＧの主成分であるイソブタン（ｉｓｏ−Ｃｅ
Ｈ＋。）に対する感度もある程度低くおさえられており
望ましい特性を持っている。ちなみに、アルカリ金属の
酸化物（Ｋ２Ｏ，ＲｂＪ、Ｃ３ｌＯ）の添加の場合はＣ
ｕＯの添加によって、好ましい結果は得られなかった。In addition, isobutane (iso-Ce) is the main component of LPG.
H+. ) is also suppressed to a certain degree, which is a desirable characteristic. By the way, in the case of adding alkali metal oxides (K2O, RbJ, C3lO), C
Addition of uO did not give favorable results.
前記のように、アルカリ金属及びアルカリ土類金属の酸
化物を添加したＣＯ検知用センサは、例えば、ＧＯ１１
００ｐｐの感度に対して数倍から１０倍程度のアルコー
ル感度を持ち、実際、活性炭などのフィルターでセンサ
をおおうことによってアルコールを除去できるがこのア
ルコール感度を低くおさえることは、使用上望ましいと
ころ、アルカリ土類金属の酸化物に対しＣｕＯを０．０
０５〜１ｍｏ１％添加し、又はアルカリ土類金属とアル
カリ金属酸化物の併用系でＣｕＯを０．００５〜１ｍｏ
１％添加することにより、アルコール感度を低くおさえ
ることができる効果があった。As mentioned above, the CO detection sensor to which alkali metal and alkaline earth metal oxides are added is, for example, GO11.
The alcohol sensitivity is several to 10 times higher than the sensitivity of 0.00 pp. In fact, alcohol can be removed by covering the sensor with a filter such as activated carbon, but it is desirable to keep this alcohol sensitivity low in terms of use. 0.0 CuO for earth metal oxides
Adding 0.05 to 1 mo of CuO, or adding 0.005 to 1 mo of CuO in a combined system of alkaline earth metal and alkali metal oxide.
Addition of 1% had the effect of keeping alcohol sensitivity low.
図は本発明の実施例を示し、第１図はガスセンサの正面
図、第２図はその一部分についての拡大断面図、第３図
ガスセンサを組込んだ回路、第４図乃至第９図は性能を
示したグラフである。
（１）・・・・・・貴金属コイル、（２） 、 （６）
・・・・・・半導体部、（３）・・・・・・アルカリ金
属酸化物の微粒、（４）・・・・・・酸化スズの粒、（
５）・・・・・・ガスセンサ。The figures show an embodiment of the present invention, in which Fig. 1 is a front view of the gas sensor, Fig. 2 is an enlarged sectional view of a portion thereof, Fig. 3 is a circuit incorporating the gas sensor, and Figs. 4 to 9 show performance. This is a graph showing (1)...Precious metal coil, (2), (6)
... Semiconductor part, (3) ... Fine grains of alkali metal oxide, (4) ... Tin oxide grains, (
5)...Gas sensor.
Claims (4)
トロンチウム及びバリウムの中から選ばれた少なくとも
１種のアルカリ土類金属の酸化物が、１．０ｍｏｌ％以
上添加されていることを特徴とする一酸化炭素ガスセン
サ。(1) Monoxide characterized in that 1.0 mol% or more of an oxide of at least one alkaline earth metal selected from beryllium, calcium, strontium, and barium is added to a tin oxide semiconductor. Carbon gas sensor.
トロンチウム及びバリウムの中から選ばれた少なくとも
１種のアルカリ土類金属の酸化物が１．０ｍｏｌ％以上
と、ナトリウム、カリウム、ルビジウム及びカルシウム
の中から選ばれた少なくとも１種のアルカリ金属の酸化
物が０．５ｍｏｌ％以上とが、それぞれ添加されている
ことを特徴とする一酸化炭素ガスセンサ。(2) The tin oxide semiconductor contains 1.0 mol% or more of an oxide of at least one alkaline earth metal selected from beryllium, calcium, strontium, and barium, and at least 1.0 mol% of an oxide selected from among sodium, potassium, rubidium, and calcium. A carbon monoxide gas sensor, characterized in that 0.5 mol% or more of an oxide of at least one selected alkali metal is added.
トロンチウム及びバリウムの中から選ばれた少なくとも
１種のアルカリ土類金属の酸化物が１．０ｍｏｌ％以上
と、酸化第二銅が０．０５〜１．０ｍｏｌ％とが、それ
ぞれ添加されていることを特徴とする一酸化炭素ガスセ
ンサ。(3) The tin oxide semiconductor contains 1.0 mol% or more of an oxide of at least one alkaline earth metal selected from beryllium, calcium, strontium, and barium, and 0.05 to 1 mol% of cupric oxide. A carbon monoxide gas sensor characterized in that .0 mol % is added to the carbon monoxide gas sensor.
トロンチウム及びバリウムの中から選ばれた少なくとも
１種のアルカリ土類金属の酸化物が１．０ｍｏｌ％以上
と、ナトリウム、カリウム、ルビジウム及びカルシウム
の中から選ばれた少なくとも１種のアルカリ金属の酸化
物が０．５ｍｏｌ％以上と、酸化第二銅が０．０５〜１
．０ｍｏｌ％とが、それぞれ添加されていることを特徴
とする一酸化炭素ガスセンサ。(4) The tin oxide semiconductor contains 1.0 mol% or more of an oxide of at least one alkaline earth metal selected from beryllium, calcium, strontium, and barium, and at least 1.0 mol% of an oxide selected from among sodium, potassium, rubidium, and calcium. The oxide of at least one selected alkali metal is 0.5 mol% or more, and the cupric oxide is 0.05 to 1 mol%.
．． A carbon monoxide gas sensor characterized in that 0 mol% is added.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19021386A JPS6345552A (en) | 1986-08-13 | 1986-08-13 | Gaseous carbon monoxide sensor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19021386A JPS6345552A (en) | 1986-08-13 | 1986-08-13 | Gaseous carbon monoxide sensor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6345552A true JPS6345552A (en) | 1988-02-26 |
| JPH0551096B2 JPH0551096B2 (en) | 1993-07-30 |
Family
ID=16254348
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19021386A Granted JPS6345552A (en) | 1986-08-13 | 1986-08-13 | Gaseous carbon monoxide sensor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6345552A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0466858A (en) * | 1990-07-06 | 1992-03-03 | New Cosmos Electric Corp | Carbon monoxide gas sensor |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8393196B2 (en) | 2007-12-14 | 2013-03-12 | Ngk Spark Plug Co., Ltd. | Gas sensor |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50132995A (en) * | 1974-04-01 | 1975-10-21 |
-
1986
- 1986-08-13 JP JP19021386A patent/JPS6345552A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50132995A (en) * | 1974-04-01 | 1975-10-21 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0466858A (en) * | 1990-07-06 | 1992-03-03 | New Cosmos Electric Corp | Carbon monoxide gas sensor |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0551096B2 (en) | 1993-07-30 |
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