JPS6224378B2 - - Google Patents
Info
- Publication number
- JPS6224378B2 JPS6224378B2 JP54126393A JP12639379A JPS6224378B2 JP S6224378 B2 JPS6224378 B2 JP S6224378B2 JP 54126393 A JP54126393 A JP 54126393A JP 12639379 A JP12639379 A JP 12639379A JP S6224378 B2 JPS6224378 B2 JP S6224378B2
- Authority
- JP
- Japan
- Prior art keywords
- gas
- sensitive body
- added
- moo
- present
- 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.)
- Expired
Links
- 239000007789 gas Substances 0.000 claims description 82
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 6
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 6
- 229910001887 tin oxide Inorganic materials 0.000 claims description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 14
- 230000035945 sensitivity Effects 0.000 description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 239000001282 iso-butane Substances 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 6
- 238000001514 detection method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000007257 malfunction Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Description
【発明の詳細な説明】
本発明は、可燃性ガスの如き還元性ガス、例え
ばイソブタンガスの存在を検知するに好適な感ガ
ス体に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a gas-sensitive body suitable for detecting the presence of a reducing gas such as a combustible gas, such as isobutane gas.
酸化錫、酸化亜鉛の如きＮ型金属酸化物半導体
を感ガス体とし、可燃性ガスと接触した際該感ガ
ス体の電導度が大きくなる特性を利用したガス検
知素子が提案されている。 BACKGROUND ART A gas sensing element has been proposed that uses an N-type metal oxide semiconductor such as tin oxide or zinc oxide as a gas sensitive body and utilizes the property that the electrical conductivity of the gas sensitive body increases when it comes into contact with a combustible gas.
かゝるガス検知素子に使用される感ガス体は可
燃性ガスの存在しない雰囲気中でも温度や湿度に
よつて日々その電導度が変動する所謂日差変動が
ある。従つて、かゝるガス検知素子に於いては、
検出すべきガスと接触したときの感ガス体の電導
度変化が、上記日差変動に対し充分に大きい感ガ
ス体即ちガス感度に優れた感ガス体を使用するこ
とによつて、始めて可燃性ガスの存在が確実に検
知できる。 The gas-sensitive body used in such a gas detection element has a so-called diurnal variation in its electrical conductivity, which varies day by day depending on temperature and humidity even in an atmosphere free of flammable gas. Therefore, in such a gas detection element,
By using a gas-sensitive material whose electrical conductivity changes when it comes into contact with the gas to be detected is sufficiently large for the above-mentioned daily variation, that is, by using a gas-sensitive material with excellent gas sensitivity, it is possible to detect flammability for the first time. The presence of gas can be detected reliably.
しかるに、従来提案されている感ガス体は、上
記ガス感度に劣り、さらに特開昭51―132893号の
感ガス体のように添加物によつてガス感度を向上
しても、ガス警報器として使用した場合、温度や
特に湿度による日差変動によつて可燃性ガスが存
在しても警報を出さなかつたり、或は該ガスが存
在しないにも拘ず警報を出す所謂誤動作する恐れ
があり、実用上満足すべき感ガス体はなかつた。 However, the gas-sensitive bodies that have been proposed so far are inferior to the above-mentioned gas sensitivity, and even if the gas sensitivity is improved by adding additives like the gas-sensitive body of JP-A-51-132893, they cannot be used as gas alarms. When used, there is a risk of so-called malfunctions in which the device does not issue an alarm even if flammable gas is present, or issues an alarm even though the gas is not present, due to daily fluctuations due to temperature and especially humidity. There was no gas-sensitive body that was practically satisfactory.
本発明は、上記難点に鑑みなされたもので、プ
ロパンガス、イソブタンガスの如き還元性ガスに
対するガス感度に優れた感ガス体の提供を目的と
する。即ち、本発明は、錫の酸化物をSnO2に換
算して100ｇに対して、Cr及び／又はその酸化物
をCr2O3に換算して0.1〜30ｇと、Mo及び／又は
その酸化物をMoO3に換算して0.5〜12ｇとを添加
してなることを特徴とする還元性ガス用感ガス体
である。 The present invention was made in view of the above-mentioned difficulties, and an object of the present invention is to provide a gas-sensitive body having excellent gas sensitivity to reducing gases such as propane gas and isobutane gas. That is, the present invention provides 0.1 to 30 g of Cr and/or its oxide in terms of Cr 2 O 3 and Mo and/or its oxide for 100 g of tin oxide in terms of SnO 2 . This is a gas-sensitive material for reducing gas, characterized in that 0.5 to 12 g of MoO 3 is added.
本発明による感ガス体は、還元性ガスに対する
ガス感度に優れ、かつ温度、湿度に対する目差変
動が少ないため、可燃性ガスの存在を検知するガ
ス警報器等に使用すると、該ガスの存在するとき
は確実に警報を出し、又該ガスの存在しないとき
に警報を出すようなことがなく、極めて信頼性の
あるガス警報器とすることができる。 The gas-sensitive body according to the present invention has excellent gas sensitivity to reducing gases and has little variation in tolerance due to temperature and humidity. It is possible to provide an extremely reliable gas alarm device that reliably issues an alarm when the gas is present, and does not issue an alarm when the gas is not present.
本発明においては、Ｎ型金属酸化物半導体に錫
の酸化物を使用しているため、比較的低温度でガ
ス感度を有するため、省エネルギーという特長も
有している。 In the present invention, since tin oxide is used as the N-type metal oxide semiconductor, it has gas sensitivity at a relatively low temperature, so it also has the advantage of energy saving.
又、該半導体に添加するCr及び／又はその酸
化物は感ガス体の電導度が還元性ガスが存在しな
いにも拘ず温度さらには湿度によつて日々変動す
る所謂該電導度の日差変動を少なくする効果を有
する。その添加量が少な過ぎると該効果が得られ
ず又、多過ぎると還元性ガスに接触したときの電
導度変化が小さくなり好ましくない。好ましい添
加量はCr2O3に換算してSnO2100ｇに対し0.1〜30
ｇの範囲であり0.5ｇ〜10ｇの範囲が特に好まし
い。 In addition, Cr and/or its oxides added to the semiconductor cause the so-called diurnal variation in the conductivity, in which the conductivity of the gas-sensitive body fluctuates daily depending on temperature and even humidity even in the absence of reducing gas. It has the effect of reducing If the amount added is too small, the effect cannot be obtained, and if the amount added is too large, the change in electrical conductivity upon contact with a reducing gas becomes small, which is not preferable. The preferable addition amount is 0.1 to 30 per 100 g of SnO 2 in terms of Cr 2 O 3
g, and a range of 0.5 g to 10 g is particularly preferred.
又、半導体に添加するMo及び／又はその酸化
物は感ガス体が還元性ガスに接触したとき、その
電導度が大きく変化する所謂還元性ガスに対する
感ガス体のガス感度を向上させる効果を有する。
その添加量が少な過ぎると上記効果が得られず
又、多過ぎると感ガス体の電導度が時間の経過と
共に小さくなる経時変化を生じ好ましくない。
Mo及び／又はその酸化物の添加量は、MoO3に換
算し、SnO2100ｇに対しMoO30.5〜12ｇの範囲が
好ましく、１〜６ｇの範囲が特に好ましい。 Furthermore, Mo and/or its oxides added to the semiconductor have the effect of improving the gas sensitivity of the gas-sensitive body to so-called reducing gases, whose electrical conductivity changes greatly when the gas-sensitive body comes into contact with reducing gas. .
If the amount added is too small, the above-mentioned effects cannot be obtained, and if it is too large, the electrical conductivity of the gas-sensitive body will change over time, which is undesirable.
The amount of Mo and/or its oxide added is preferably in the range of 0.5 to 12 g, particularly preferably 1 to 6 g, of MoO 3 per 100 g of SnO 2 in terms of MoO 3 .
本発明による感ガス体を使用し、ガス検知素子
を製造するに当つては例えば次の方法がある。 For example, the following method can be used to manufacture a gas sensing element using the gas-sensitive body according to the present invention.
SnO2，Cr2O3，MoO3をそれぞれ所定量秤量
し、バインダーと混練しペースト化する。その場
合Cr2O3，MoO3はCr，Moの塩化物又は他の塩の
型であつてもよい。次いで、第１図ａの如く片面
に対向電極１の形成されたアルミナ基板２に上記
ペーストをスクリーン印刷し、該電極間に膜状の
感ガス体３を形成する。尚、アルミナ基板の反対
面には第１図ｂの如くヒーター４が形成してあ
る。次いで、この感ガス体を形成したアルミナ基
板を焼成し、ガス検知素子が製造される。 Predetermined amounts of SnO 2 , Cr 2 O 3 , and MoO 3 are each weighed and kneaded with a binder to form a paste. In that case, Cr 2 O 3 , MoO 3 may be in the form of chlorides or other salts of Cr, Mo. Next, as shown in FIG. 1A, the above paste is screen printed on an alumina substrate 2 having a counter electrode 1 formed on one side, thereby forming a film-like gas-sensitive body 3 between the electrodes. Incidentally, a heater 4 is formed on the opposite surface of the alumina substrate as shown in FIG. 1b. Next, the alumina substrate on which the gas-sensitive body is formed is fired to produce a gas sensing element.
実施例 １
SnO2の半導体粒子100ｇに対し、Cr2O3，MoO3
をそれぞれ２ｇ、３ｇの割合で添加し、更にバイ
ンダーを添加して混練しペーストを作成した。次
いで、第１図ａの如く対向電極の形成されたアル
ミナ基板に該ペーストを印刷し、該電極間に膜状
の感ガス体を形成した後焼成して、第１図の如き
ガス検知素子を製造した。（アルミナ基板の反対
面には、第１図ｂの如きヒータが形成してあ
る。）次いで、この素子の特性を第２図の回路に
よつて調べた。図に於いて、Rxは感ガス体の抵
抗、Rhは感ガス体を加熱するためのアルミナ基
板の反対面に形成したヒータの抵抗、ＲLはRxに
直列に接続した抵抗であり、ヒータに所定の電流
を供給し感ガス体を加熱しておき、感ガス体の電
導度をＲLの両端電圧として測定した。Example 1 Cr 2 O 3 , MoO 3 for 100 g of SnO 2 semiconductor particles
were added at a ratio of 2 g and 3 g, respectively, and a binder was further added and kneaded to prepare a paste. Next, the paste is printed on an alumina substrate on which a counter electrode is formed as shown in FIG. Manufactured. (A heater as shown in FIG. 1b is formed on the opposite side of the alumina substrate.) Next, the characteristics of this element were investigated using the circuit shown in FIG. 2. In the figure, Rx is the resistance of the gas-sensitive body, Rh is the resistance of the heater formed on the opposite side of the alumina substrate for heating the gas-sensitive body, and R L is the resistance connected in series with Rx. A predetermined current was supplied to heat the gas-sensitive body, and the electrical conductivity of the gas-sensitive body was measured as the voltage across R L .
このガス検知素子をイソブタンガス中に入れ、
該ガス濃度を変えて出力電圧を測定した。その結
果を第３図の実線で示す。 Put this gas detection element into isobutane gas,
The output voltage was measured while changing the gas concentration. The results are shown by the solid line in FIG.
この素子と比較する為、感ガス体にMoO3を添
加しない外は実施例と全く同じものを製造し、実
施例と同じ測定をした。その結果を第３図の点線
に示した。第３図から明らかな如く、本発明によ
る感ガス体はMoO3無添加のものに比べイソブタ
ンガスに接触した際大きな出力電圧変化が得ら
れ、所謂るガス感度に優れていることが判つた。 In order to compare with this device, a device was manufactured that was exactly the same as in the example except that MoO 3 was not added to the gas-sensitive body, and the same measurements as in the example were conducted. The results are shown in the dotted line in FIG. As is clear from FIG. 3, the gas-sensitive element according to the present invention obtained a larger change in output voltage when it came into contact with isobutane gas than the one without MoO 3 added, and was found to have excellent so-called gas sensitivity.
実施例 ２
SnO2の半導体粒子100ｇに対し、Cr2O3，MoO3
をそれぞれ２ｇ、５ｇの割で添加し実施例１と同
様の素子を製造し、同様の測定をした。その結果
を第３図の一点鎖線で示した。この結果、この素
子はイソブタンガスに対するガス感度が、
MoO33ｇ添加したものより若干低いがMoO3無添
加のものより高かつた。Example 2 Cr 2 O 3 , MoO 3 for 100 g of SnO 2 semiconductor particles
The same elements as in Example 1 were manufactured by adding 2 g and 5 g of each of these, and the same measurements were carried out. The results are shown by the dashed line in FIG. As a result, this element's gas sensitivity to isobutane gas is
It was slightly lower than the one with 3g of MoO 3 added, but higher than the one without MoO 3 added.
実施例 ３
本発明による感ガス体の日差変動を調べる為、
実施例１によつて製造した素子を0.1％および0.3
％濃度のイソブタンガス中に入れ、その出力電圧
を調べた。その結果を第４図の実線で示す。一
方、比較の為感ガス体にCr2O3を添加しない外は
実施例１と同様の素子を製造し、同様の実験を行
なつた結果を同図の点線で示した。尚、図中ａ，
ｂはそれぞれにイソブタンガス濃度0.3％、0.1％
の時の値である。この結果Cr2O3を添加した素子
は日々の出力電圧の変動即ち日差変動が極めて少
ないことが判明した。Example 3 In order to investigate the daily variation of the gas-sensitive body according to the present invention,
0.1% and 0.3% of the device manufactured according to Example 1
% concentration of isobutane gas, and its output voltage was examined. The results are shown by the solid line in FIG. On the other hand, for comparison, an element similar to that of Example 1 was manufactured except that Cr 2 O 3 was not added to the gas-sensitive body, and the same experiment was conducted. The results are shown by the dotted line in the figure. In addition, in the figure a,
b is isobutane gas concentration 0.3% and 0.1% respectively
This is the value when . As a result, it was found that the element doped with Cr 2 O 3 had very little daily fluctuation in output voltage, that is, daily fluctuation.
以上のように、本発明の感ガス体は、Ｎ型金属
酸化物半導体であるSnO2100ｇに対し、Cr及び／
又はその酸化物をCr2O3に換算して0.1〜30ｇと、
Mo及び／又はその酸化物をMoO3に換算して0.5
〜12ｇとを添加して形成したため、SnO2を母体
材料とした各添加剤との組成比により、還元性ガ
スに対するガス感度を優れたものとし、さらには
温度や湿度に起因する日差変動を少なくして誤動
作を防ぐことのできる極めて信頼性のある感ガス
体とすることができる。 As described above, the gas-sensitive body of the present invention contains Cr and/ or
or 0.1 to 30 g of the oxide in terms of Cr 2 O 3 ,
Mo and/or its oxide converted to MoO 3 0.5
~12g of SnO2 is added to the base material, and the composition ratio with each additive with SnO 2 as the base material provides excellent gas sensitivity to reducing gases, and also reduces daily fluctuations caused by temperature and humidity. It is possible to obtain an extremely reliable gas-sensitive body that can prevent malfunctions by reducing the number of gases.
第１図は本発明の感ガス体を用いたガス検知素
子の平面図である。第２図はガス検知素子の特性
を測定する為の回路図である。第３図，第４図は
感ガス体の特性を測定した結果を示すグラフであ
る。
１……電極、２……アルミナ基板、３……感ガ
ス体、４……ヒーター。
FIG. 1 is a plan view of a gas sensing element using the gas-sensitive body of the present invention. FIG. 2 is a circuit diagram for measuring the characteristics of the gas detection element. FIGS. 3 and 4 are graphs showing the results of measuring the characteristics of the gas-sensitive body. 1... Electrode, 2... Alumina substrate, 3... Gas sensitive body, 4... Heater.
Claims (1)
て、Cr及び／又はその酸化物をCr2O3に換算して
0.1〜30ｇと、Mo及び／又はその酸化物をMoO3
に換算して0.5〜12ｇとを添加してなることを特
徴とする還元性ガス用感ガス体。1 Cr and/or its oxide is converted to Cr 2 O 3 per 100g of tin oxide converted to SnO 2
0.1 to 30 g of Mo and/or its oxides as MoO 3
A gas-sensitive material for reducing gases, characterized in that 0.5 to 12 g is added in terms of .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12639379A JPS5650168A (en) | 1979-10-02 | 1979-10-02 | Gas sensing body for reducing gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12639379A JPS5650168A (en) | 1979-10-02 | 1979-10-02 | Gas sensing body for reducing gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5650168A JPS5650168A (en) | 1981-05-07 |
| JPS6224378B2 true JPS6224378B2 (en) | 1987-05-28 |
Family
ID=14934021
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12639379A Granted JPS5650168A (en) | 1979-10-02 | 1979-10-02 | Gas sensing body for reducing gas |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5650168A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR870001786B1 (en) * | 1982-01-29 | 1987-10-10 | 카다 야마히도 하지로 | Combined air conditioning and hot water service system |
| JPS61186068U (en) * | 1985-05-10 | 1986-11-20 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51132893A (en) * | 1975-05-14 | 1976-11-18 | Toshiba Corp | Gas sensitive body |
-
1979
- 1979-10-02 JP JP12639379A patent/JPS5650168A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51132893A (en) * | 1975-05-14 | 1976-11-18 | Toshiba Corp | Gas sensitive body |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5650168A (en) | 1981-05-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4541988A (en) | Constant temperature catalytic gas detection instrument | |
| US4587104A (en) | Semiconductor oxide gas combustibles sensor | |
| JPH07134110A (en) | Combination type semiconductor gas sensitive element | |
| JPH0517650Y2 (en) | ||
| Nitta et al. | Multifunctional ceramic sensors: Humidity-gas sensor and temperature-humidity sensor | |
| JPS6224378B2 (en) | ||
| Sayago et al. | Long-term reliability of sensors for detection of nitrogen oxides | |
| EP0086415B1 (en) | Humidity sensitive device | |
| CN114384124A (en) | Anti-drift double-gas-sensitive-membrane gas sensor | |
| JPS6245495B2 (en) | ||
| KR900003929B1 (en) | Gas detector | |
| KR900003928B1 (en) | Gas detector | |
| KR900003930B1 (en) | Gas detector | |
| Ionescu et al. | Conduction—concentration relationship in chemoresistive thick-film SnO2 gas sensors | |
| KR930000542B1 (en) | Thin type element for detecting gas | |
| JPH022534B2 (en) | ||
| JPS61245049A (en) | Humidity sensor | |
| JPS60179649A (en) | Gas-sensitive body for reducing gas | |
| KR930000541B1 (en) | Thick type element for detecting gas | |
| JPS6128934B2 (en) | ||
| JPH02263145A (en) | Semiconductor type gas sensor | |
| JP3976883B2 (en) | Gas detection element | |
| JPS58168952A (en) | Gas sensitive element | |
| JP3919307B2 (en) | Hot wire semiconductor gas detector for air pollution detection | |
| JPS6140937B2 (en) |