JPS61155947A - Exhaust gas sensor - Google Patents
Exhaust gas sensorInfo
- Publication number
- JPS61155947A JPS61155947A JP28010884A JP28010884A JPS61155947A JP S61155947 A JPS61155947 A JP S61155947A JP 28010884 A JP28010884 A JP 28010884A JP 28010884 A JP28010884 A JP 28010884A JP S61155947 A JPS61155947 A JP S61155947A
- Authority
- JP
- Japan
- Prior art keywords
- exhaust gas
- gas sensor
- compound
- detection piece
- effect
- 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
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
Abstract
Description
【発明の詳細な説明】
〔発明の利用分骨〕
この発明は、金属酸化物半導体の抵抗値の変化を利用し
た排ガスセンサの材料に関する。DETAILED DESCRIPTION OF THE INVENTION [Uses of the Invention] The present invention relates to a material for an exhaust gas sensor that utilizes changes in the resistance value of a metal oxide semiconductor.
発明者は、Ｂａ５ｎＯａ等の化合物を用いた排ガスセン
サを提案した（特願昭５９−６３９００号）。The inventor proposed an exhaust gas sensor using a compound such as Ba5nOa (Japanese Patent Application No. 59-63900).
その後発明者は、５ｒＴｉＯａや５ｒ２Ｔｉ０４等の化
合物が高い酸素感度を持つことを発見した。Subsequently, the inventor discovered that compounds such as 5rTiOa and 5r2Ti04 have high oxygen sensitivity.
この発明は、排ガスセンサの酸素感度の改善を目的とす
る。This invention aims to improve the oxygen sensitivity of an exhaust gas sensor.
この発明の排ガスセンサは、化合物（ＡＯ）ｎ−Ｂ２０
、ここにＡはアルカリ土類元素の少くとも一員を、Ｂは
ＳｎおよびＴｉからなる群の少くとも一員を現わし、ｎ
≧１で有る、にアルカリ金属およびＡｙとＯｕとか・ら
、なる群の少くとも一員の元素を加えたことを特徴とす
る。The exhaust gas sensor of this invention is a compound (AO)n-B20
, where A represents at least a member of the alkaline earth elements, B represents at least a member of the group consisting of Sn and Ti, and n
≧1, and is characterized by adding at least an element of the group consisting of an alkali metal and Ay, O, etc.
このような化合物としては、ＢａＳｎＯ３、Ｒａ５ｎ０
３ 。Such compounds include BaSnO3, Ra5n0
3.
Ｃａ５ｎＯＢ 、 ５ｒＳｎ０３ 、 ＢａＴｉＯ３、
ＲａＴｉＯ３。Ca5nOB, 5rSn03, BaTiO3,
RaTiO3.
５ｒＴｉ０３ 、 ＣａＴｉＯ３、ＭｇＴｉ０Ｂ 、
５ｒ３Ｔｉ２０７゜Ｓｒ２’ｌ’ｉ０４． Ｓｒ４’ｌ
’１ａＯｔｏ 、 ＣａｓＴｉ２０７１Ｍｇ２Ｔｉ０４
。5rTi03, CaTiO3, MgTi0B,
5r3Ti207°Sr2'l'i04. Sr4'l
'1aOto, CasTi2071Mg2Ti04
.
Ｂａ２ＴｉＯ４、等が有る。これらの化合物のうら、Ｂ
ａ５ｎＯａ 、 Ｒａ５ｎＯａ 、 ＢａＴｉ０ａ 、
ＲａＴｉ０ａの４者はｎ形金属酸化物半導体で、他は
ｐ形金属酸化物半導体で有る。またこれらの化合物は単
独で、あるいは混合して、さらには成分の１部を他の元
素で置換して用いることができる。There are Ba2TiO4, etc. The back of these compounds, B
a5nOa, Ra5nOa, BaTi0a,
Four of RaTi0a are n-type metal oxide semiconductors, and the others are p-type metal oxide semiconductors. Further, these compounds can be used alone or in a mixture, and a part of the components can be replaced with other elements.
添加物の効果は酸素感度の改善に有り、アルカリ金属で
最も大きな効果が得られ、ＡｙやＣｕがこれにつぐ。添
加物の存在形態は、Ｂａ８ｎＯａや５ｒＴｉＯａ等の母
結晶のＢａやＳｒサイトの置換や格子間への固溶と、結
晶表面への析出とに有ると考えられる。固溶や置換は必
ずしも均一ではなく、結晶表面への偏析を伴うものと思
われる。添加後の組成は、ＢａＳｎＯ３へのＮａ２Ｏの
添加を例にすると、Ｂａ１−ｘＮａ＞（Ｓｎ０３でもＢ
ａｌ 、Ｎａ）（−５ｎＯａ＋ｘ７２でも良い。この場
合の過剰のＢａまたはＳｎは、ＢａＯまたは５ｎ０２
として析出する。The effect of additives is to improve oxygen sensitivity, and the greatest effect is obtained with alkali metals, followed by Ay and Cu. It is thought that the additive exists in the following ways: substituting Ba or Sr sites in the host crystal such as Ba8nOa or 5rTiOa, solid solution in the interstitial space, and precipitation on the crystal surface. Solid solution and substitution are not necessarily uniform and are thought to involve segregation on the crystal surface. Taking the addition of Na2O to BaSnO3 as an example, the composition after addition is Ba1-xNa>(B even in Sn03).
al, Na) (-5nOa+x72. In this case, excess Ba or Sn is BaO or 5n02
It precipitates as
（センサの構造）
第１図において、（２）はアルミナ等の耐熱絶縁性基体
、（４）はセンサを自動車エンジンの排気管等に挿入す
るための金属ハウジング、（６）はヒータ管でガス検出
片（８）の保護カバーを兼ねる。ヒータ管（６）はセラ
ミックス製で、内部に白金やタングステン等のヒータパ
ターン００を埋設して有る。(Structure of the sensor) In Fig. 1, (2) is a heat-resistant insulating base made of alumina, etc., (4) is a metal housing for inserting the sensor into an automobile engine exhaust pipe, etc., and (6) is a heater tube for gas Also serves as a protective cover for the detection piece (8). The heater tube (6) is made of ceramics, and has a heater pattern 00 of platinum, tungsten, etc. embedded inside.
ガス検出片（８）の材料には、Ｂａ５ｎＯＢ 、 Ｃ！
ａｓｎ０３ 。The materials of the gas detection piece (8) include Ba5nOB, C!
asn03.
等のＡＳｎＯ３型化合物、５ｒＴｉ０３ 、 ＣａＴｉ
、ＯＢ等のＡＴｉＯＢ型化合物、Ａ２ Ｔｉ ０４型化
合物、Ａ３Ｔｉ２０７型化合物、Ａ４ＴｉａＯ１ｏ型化
合物等に、アルカリ金属とＡｙおよびＣｕからなる群の
少くとも一員の元素を添加したものを用いる。ASnO3 type compounds such as 5rTi03, CaTi
, OB, etc., A2Ti04 type compound, A3Ti207 type compound, A4TiaO1o type compound, etc., to which an alkali metal and at least one member of the group consisting of Ay and Cu are added.
ガス検出片（８）には、貴金属電極（２）、Ｏ優を接続
し、リード線Ｑｆ９．Ｑ８）を介して外部と接続する。To the gas detection piece (8), connect the noble metal electrode (2) and O-type, and connect the lead wire Qf9. Connect to the outside via Q8).
（試験例）
アルカリ土類金属の炭酸塩と５ｎ０２とを等モル量混合
し、１２００°Ｃで空気中で４時間仮焼し、ＢａＳｎＯ
３、５ｒＳｎ０３ 、０ａＳｎ０３ 、 等を得た。(Test example) Alkaline earth metal carbonate and 5n02 were mixed in equimolar amounts, calcined in air at 1200°C for 4 hours, and BaSnO
3, 5rSn03, 0aSn03, etc. were obtained.
生成物のＢａＳｎＯ３等に硝酸塩としてアルカリ金属や
ＡｙやＯｕを付着させ、ガス検出片（８）の形状に成型
し、空気中で４時間１４００°Ｃに焼成した。Alkali metals, Ay, and Ou were attached as nitrates to BaSnO3 and the like of the product, which was then molded into the shape of a gas detection piece (8) and fired at 1400°C for 4 hours in air.
同様にしてアルカリ金属等を加えた、５ｒＴｉＯａやＣ
ａＴｉＯ３等と、５ｒ３Ｔｉ２０７． Ｓｒ２’ｌ’ｉ
０４ 等を得た。焼成条件はＡＴｉＯａ形化合物につい
て、仮焼を１２００°Ｃ１焼成をｉ ａ ｏ ｏ ’ｃ
とし、Ａ２ＴｉＯ４゜Ａ３Ｔｉ２０７ 、 Ａ４Ｔｉａ
Ｏｔｏ型化合物について、仮焼と焼成とを各１４００°
Ｃとした。Similarly, 5rTiOa and C were added with alkali metal etc.
aTiO3 etc., and 5r3Ti207. Sr2'l'i
04 etc. were obtained. The firing conditions are: ATiOa type compound, calcination at 1200°C1.
and A2TiO4゜A3Ti207, A4Tia
For Oto-type compounds, calcination and firing were performed at 1400° each.
It was set as C.
アルカリ金属やＡｙ、Ｃｕの添加は、半導体の抵抗値や
抵抗温度係数にはあまり影響しなかった。The addition of alkali metals, Ay, and Cu did not significantly affect the resistance value and temperature coefficient of resistance of the semiconductor.
つぎに各ガス検出片（８）の酸素感度を測定した。Next, the oxygen sensitivity of each gas detection piece (8) was measured.
７００°ＣのＮ２バランＺで０２濃度を１から１０％へ
増して抵抗値を測定し、
Ｒｓ＝Ｋ Ｐｏ２
として酸素勾配（ｎ）を定義し、ｎにより結果を示す。Resistance values are measured with increasing O2 concentration from 1 to 10% in N2 balun Z at 700°C, oxygen gradient (n) is defined as Rs=K Po2 and results are expressed by n.
第２図〜第４図と表１とに、結果を示す。The results are shown in FIGS. 2 to 4 and Table 1.
各図から明らかなように、０．０２ ｗｔ％の添加で酸
素感度は改善される。なおここでｗｔ％単位として、添
加物を、Ｎａ２Ｏ，Ｌｉ２Ｏ，Ｎ２０． Ｃｓ２Ｏ。As is clear from each figure, the oxygen sensitivity is improved by adding 0.02 wt%. Here, the additives are expressed as Na2O, Li2O, N20. Cs2O.
Ｒｂ２Ｏ，Ａｆ２０． （Ｅｕ２０等の１価の酸化物に
換算し、Ａｓｎ０３等の化合物Ｌｆ−当りＬＯ’１９の
添加を１ｗｔ％として表示する。添加効果は０．１ ｗ
ｔ％以上でほぼ飽和する。Rb2O, Af20. (Converted into monovalent oxide such as Eu20, the addition of LO'19 is expressed as 1 wt% per compound Lf- such as Asn03. The addition effect is 0.1 w
It is almost saturated at t% or more.
表１と第２〜第４図とを総合すると、アルカリ金属とＡ
ｙおよびＣｕの範囲で、酸素感度が改善されることがわ
かる。When Table 1 and Figures 2 to 4 are combined, alkali metals and A
It can be seen that the oxygen sensitivity is improved within the range of y and Cu.
表１゜
１” Ｂａ８ｎＯＢ ・・・・・・・０．１
８２ ｔｔ Ｌ１２０ ０
．１ ０．２０８ ’／
０８２０ ０．１ ０．２１４ １
０ｕ２０ ０．１． ０．１９５’
ＲａＳｎ０ｇ ＝” ０．１９６
” Ｎ５Ｌ２０ ０．１
０．２２７’ ８ｒＳｎＯＢ ””
−０，１２８Ｉ Ｎａｇｏ ０．
１ −０．１４９’ Ｏａ８ｎＯｇ ＝
−０゜１５１０ １
Ｎａｚｏ ０．１ −０．１７※
１１ ８ｒＴｉＯｇ −・・−０，
２１１２’／ Ｌｉ、２０ ０．１ −
０．２８１８ １ ０５ｇ０
０．１ −０．２４１４ ＃
０１１２０ ０．１ −０．２８※
１５ ０ａ’ｆ’ｉ０３ ｍ＋＋
−０，２１１６１Ｎａ２Ｏ０，１−０，２８
※
１７ ５ｒａＴｉ２０ｙ ・・・・”
−０，２２１８／／ Ｎａｚｏ
０．１ −０．２５表１．つづき
※
１９ Ｓｒ＋ＴｉａＯｔｏ ・・・・・
・−０，２２２０／／ Ｎａ２Ｏ０，１−０，
２５２１’ ０ａａＴｉ２０７ − −
０．２２２２ ｌ Ｋｉｏ ０
．１ −０．２４※
２８ ＭｙｚＴｉ０４ ・・・・・・
−〇、２１２４ ｌ Ｎａ２Ｏ
０，１−０，２８※
２５ ＢａｇＴｉＯ４・・・・・・ −〇
、１６２６ １ Ｎａｎｏ Ｏ，１
−０，１９２７ｌ ＴＬｂ２０ ０．１
０．１８２８ ８ｒＦｅＯａ※２ 、、、、、
、 −０．１１※
※ ※２
２９ ａｒＦｅＯＢ Ｎａ２Ｏ０，１−０
，１１※１ ※印は比較例。Table 1゜1” Ba8nOB ・・・・・・0.1
82 tt L120 0
．． 1 0.208'/
0820 0.1 0.214 1
0u20 0.1. 0.195'
RaSn0g =” 0.196
” N5L20 0.1
0.227' 8rSnOB ""
-0,128I Nago 0.
1 -0.149' Oa8nOg =
-0°1510 1
Nazo 0.1 -0.17* 11 8rTiOg -・・-0,
2112'/Li, 20 0.1-
0.2818 1 05g0
0.1 -0.2414 #
01120 0.1 -0.28* 15 0a'f'i03 m++
-0,21161Na2O0,1-0,28 *17 5raTi20y ・・・・”
-0,2218// Nazo
0.1 -0.25Table 1. Continued※ 19 Sr+TiaOto...
・-0,2220// Na2O0,1-0,
2521' 0aaTi207 - -
0.2222 l Kio 0
．． 1 -0.24* 28 MyzTi04 ・・・・・・
-〇, 2124 l Na2O
0,1-0,28* 25 BagTiO4... -〇, 1626 1 Nano O,1
-0,1927l TLb20 0.1
0.1828 8rFeOa*2 ,,,,,
, -0.11* * *2 29 arFeOB Na2O0,1-0
,11*1 ※marks are comparative examples.
※２ １２００℃で仮焼後、１８００℃で焼成。*2 After calcination at 1200℃, firing at 1800℃.
この発明では、排ガスセンサの酸素感度を改善すること
ができる。゛With this invention, the oxygen sensitivity of the exhaust gas sensor can be improved.゛
第１図は実施例の排ガスセンサの長手方向断面図で、第
２図〜第４図は実施例の排ガスセンサの特性図で有る。
特許出願人 フィガロ技研株式会社第１図
第２図
０ ０．０１ ０．１ １．０ｗｔ（’１０）
第３図
０ ０．０１ ０．１ １．０第４図FIG. 1 is a longitudinal sectional view of the exhaust gas sensor of the embodiment, and FIGS. 2 to 4 are characteristic diagrams of the exhaust gas sensor of the embodiment. Patent applicant Figaro Giken Co., Ltd. Figure 1 Figure 2 0 0.01 0.1 1.0wt ('10) Figure 3 0 0.01 0.1 1.0 Figure 4
Claims (1)
リ土類元素の少くとも一員を、ＢはＳｎおよびＴｉから
なる群の少くとも一員を現し、ｎ≧１で有る、にＬｉ、
Ｎａ、Ｋ、Ｒｂ、Ｃｓ、Ａｇ、およびＣｕからなる群の
少くとも一員の元素を添加したことを特徴とする排ガス
センサ。(1) Compound (AO)n・BO_2, where A represents at least a member of the alkaline earth elements, B represents at least a member of the group consisting of Sn and Ti, and n≧1, Li,
An exhaust gas sensor characterized in that at least one element of the group consisting of Na, K, Rb, Cs, Ag, and Cu is added.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28010884A JPS61155947A (en) | 1984-12-28 | 1984-12-28 | Exhaust gas sensor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28010884A JPS61155947A (en) | 1984-12-28 | 1984-12-28 | Exhaust gas sensor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61155947A true JPS61155947A (en) | 1986-07-15 |
| JPH053899B2 JPH053899B2 (en) | 1993-01-18 |
Family
ID=17620430
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28010884A Granted JPS61155947A (en) | 1984-12-28 | 1984-12-28 | Exhaust gas sensor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61155947A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4911914A (en) * | 1986-09-29 | 1990-03-27 | Kazuko Satake | Method for producing an exhaust gas sensor |
| US5070318A (en) * | 1988-03-15 | 1991-12-03 | Figaro Engineering, Inc. | Exhaust gas sensor and process for producing same |
| JPH0769285B2 (en) * | 1987-07-11 | 1995-07-26 | ロート―テヒニーク ゲゼルシャフト ミット ベシュレンクテル ハフツング ウント コンパニー フォルシュング フュア アウトモビール― ウント ウムヴェルトテヒニーク | Semiconductor for resistive gas sensor with high response speed |
| GB2342451A (en) * | 1998-07-07 | 2000-04-12 | Bacharach Inc | Halogen gas detector |
| CN104641422A (en) * | 2013-03-29 | 2015-05-20 | 瑞福龙株式会社 | Transparent compound semiconductor and P-type doping method therefor |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4929186A (en) * | 1972-07-08 | 1974-03-15 | ||
| JPS49135695A (en) * | 1973-04-27 | 1974-12-27 | ||
| JPS5115492A (en) * | 1974-07-29 | 1976-02-06 | Hitachi Ltd | Kemuri oyobi gasukenchisoshi |
| JPS51125685A (en) * | 1974-11-12 | 1976-11-02 | Matsushita Electric Ind Co Ltd | Oxidation catalyst for inflammable gas |
| JPS5689048A (en) * | 1979-12-21 | 1981-07-20 | Matsushita Electric Ind Co Ltd | Exhaust gas sensor |
-
1984
- 1984-12-28 JP JP28010884A patent/JPS61155947A/en active Granted
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4929186A (en) * | 1972-07-08 | 1974-03-15 | ||
| JPS49135695A (en) * | 1973-04-27 | 1974-12-27 | ||
| JPS5115492A (en) * | 1974-07-29 | 1976-02-06 | Hitachi Ltd | Kemuri oyobi gasukenchisoshi |
| JPS51125685A (en) * | 1974-11-12 | 1976-11-02 | Matsushita Electric Ind Co Ltd | Oxidation catalyst for inflammable gas |
| JPS5689048A (en) * | 1979-12-21 | 1981-07-20 | Matsushita Electric Ind Co Ltd | Exhaust gas sensor |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4911914A (en) * | 1986-09-29 | 1990-03-27 | Kazuko Satake | Method for producing an exhaust gas sensor |
| JPH0769285B2 (en) * | 1987-07-11 | 1995-07-26 | ロート―テヒニーク ゲゼルシャフト ミット ベシュレンクテル ハフツング ウント コンパニー フォルシュング フュア アウトモビール― ウント ウムヴェルトテヒニーク | Semiconductor for resistive gas sensor with high response speed |
| US5070318A (en) * | 1988-03-15 | 1991-12-03 | Figaro Engineering, Inc. | Exhaust gas sensor and process for producing same |
| GB2342451A (en) * | 1998-07-07 | 2000-04-12 | Bacharach Inc | Halogen gas detector |
| GB2342451B (en) * | 1998-07-07 | 2003-08-13 | Bacharach Inc | Halogen gas detector |
| CN104641422A (en) * | 2013-03-29 | 2015-05-20 | 瑞福龙株式会社 | Transparent compound semiconductor and P-type doping method therefor |
| JP2015533752A (en) * | 2013-03-29 | 2015-11-26 | アールエフトロン カンパニー リミテッドＲｆｔｒｏｎ Ｃｏ．，Ｌｔｄ． | Transparent compound semiconductor and p-type doping method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH053899B2 (en) | 1993-01-18 |
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