JPS589376B2 - gas sensing element - Google Patents
gas sensing elementInfo
- Publication number
- JPS589376B2 JPS589376B2 JP5596575A JP5596575A JPS589376B2 JP S589376 B2 JPS589376 B2 JP S589376B2 JP 5596575 A JP5596575 A JP 5596575A JP 5596575 A JP5596575 A JP 5596575A JP S589376 B2 JPS589376 B2 JP S589376B2
- Authority
- JP
- Japan
- Prior art keywords
- gas
- sensitive
- present
- resistance value
- sensitive element
- 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
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- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Description
【発明の詳細な説明】
本発明は酸化物焼結体の感ガス体を用いる感ガス素子に
関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a gas-sensitive element using a gas-sensitive body made of an oxide sintered body.
従来のＳｎＯ２系感ガス体を用いた感ガス素子にあって
は、ガス濃度に対して直線的な抵抗変化の得られるもの
は、その抵抗変化率が小さく、検出装置で大きな出力を
取り出しにくい。Among conventional gas-sensitive elements using SnO2-based gas-sensitive bodies, those that can obtain a linear resistance change with respect to gas concentration have a small resistance change rate, making it difficult to extract a large output with a detection device.
また抵抗変化率の大きなものであっては、その直線性が
悪く少量のガスで抵抗変化が飽和してしまい、事故によ
るガスが器具使用時のガスかの区別ができず扱いすらい
ものであった。In addition, if the resistance change rate is large, the linearity is poor and the resistance change becomes saturated with a small amount of gas, making it difficult to distinguish between the gas caused by an accident and the gas generated during use of the device. .
さらにプロパンガス、ブタンガスなどの液化石油ガスと
Ｈ２，Ｃｏなとのガスとの区別ができず、タバコの煙な
どの還元成分で抵抗変化を生じてしまうなどの多くの欠
点があった。Furthermore, there were many drawbacks such as the inability to distinguish between liquefied petroleum gases such as propane gas and butane gas and gases such as H2 and Co, and resistance changes caused by reducing components such as cigarette smoke.
本発明は上述した従来の欠点を改良したもので、モル比
組成でＺｎＯを９９．８５〜２０％、Ｍｅ１２を０．１
〜５０％（ただし、Ｍｅ１はＴｉ，ＺｒｓＨｆ，Ｓｎ，
Ｇｅのうち少なくとも一種）およびＭｅ２２Ｏ３を０．
０５〜３０％（ただし、Ｍｅ２はＧａ，Ｂ，Ｉｎ，Ｆｅ
，Ａｌ，Ｃｒのうち少なくとも一種）を含む焼結体から
なる感ガス体を用いることにより、信頼性の高い感ガス
素子を提供することを目的とする。The present invention improves the above-mentioned conventional drawbacks, and has a molar ratio of ZnO of 99.85 to 20% and Me12 of 0.1%.
~50% (However, Me1 is Ti, ZrsHf, Sn,
at least one of Ge) and Me22O3.
05-30% (However, Me2 is Ga, B, In, Fe
An object of the present invention is to provide a highly reliable gas-sensitive element by using a gas-sensitive body made of a sintered body containing at least one of , Al, and Cr.
本発明による感ガス素子は上記組成の感ガス体を一対の
電極間に設け、感ガス体の電気抵抗の変化をこの電極に
て電気信号としてとりだすことによりガス検知を行なう
ものである。The gas-sensitive element according to the present invention detects gas by disposing a gas-sensitive body having the above-mentioned composition between a pair of electrodes and extracting a change in the electrical resistance of the gas-sensitive body as an electric signal using the electrodes.
本発明による感ガス素子は例えば第１図に示すような構
造をとる。The gas-sensitive element according to the present invention has a structure as shown in FIG. 1, for example.
この感ガス素子１は円柱状のセラミック性絶縁基板２０
表面に金属線の一対の電極３，４を平行させて巻回し、
この巻回部に感ガス体５塗着焼結して固着してある。This gas-sensitive element 1 has a cylindrical ceramic insulating substrate 20.
A pair of metal wire electrodes 3 and 4 are wound in parallel on the surface,
A gas sensing element 5 is coated and sintered to this wound portion and fixed thereto.
この列では電極３，４の一方を感ガス体５の加熱用ヒー
タとして兼用するが、別にヒータを設けても良い。In this row, one of the electrodes 3 and 4 is also used as a heater for heating the gas-sensitive body 5, but a separate heater may be provided.
感ガス素子１は、たとえば次のようにして製造する。The gas-sensitive element 1 is manufactured, for example, as follows.
まずＺｎＯ，Ｍｅ１０２（ただし、Ｍｅ１はＴｔ，Ｚｒ
，Ｈｔ，Ｓｎ，Ｇｅのうち少なくとも一種）Ｍｅ２２Ｏ
３（ただしＭｅ２はＧａ，Ｂ，Ｉｎ，Ｆｅ，Ａｌ，Ｃｒ
のうち少なくとも一種）を所定組成比となるように秤取
し、これを混合して水またはバインダを加えてペースト
状とし、電極３，４の巻回部に塗着し、乾燥したのち６
００℃〜８００℃で焼成して焼結体を造る。First, ZnO, Me102 (however, Me1 is Tt, Zr
, Ht, Sn, Ge) Me22O
3 (However, Me2 is Ga, B, In, Fe, Al, Cr
(at least one of these) is weighed out to have a predetermined composition ratio, mixed, water or a binder is added to form a paste, and the paste is applied to the wound portions of the electrodes 3 and 4, dried, and then 6
A sintered body is produced by firing at a temperature of 00°C to 800°C.
この場合の焼成工程は電気炉で行っても、電極３，４の
いずれか一方にヒータとして通電して行ってもよい。The firing process in this case may be performed in an electric furnace or by applying electricity to one of the electrodes 3 and 4 as a heater.
またその雰囲気は空気中であってもよい。Further, the atmosphere may be in the air.
なお感ガス体に用いる金属酸化物ＺｎＯ，Ｍｅ１０２（
ただし、Ｍｅ１はＴｉ，Ｚｒ，Ｈｆ，Ｓｎ，Ｇｅのうち
少なくとも一種）Ｍｅ２２Ｏ３（Ｍｅ２はＧａ，Ｂ，Ｉ
ｎ，Ｆｅ，Ａｌ，Ｃｒのうち少なくとも一種）は加熱さ
れて酸化物に転じる化合物、例えば水酸化物、炭酸塩、
蓚酸塩、硝酸塩を用いることもできる。Note that the metal oxide ZnO, Me102 (
However, Me1 is at least one of Ti, Zr, Hf, Sn, Ge) Me22O3 (Me2 is Ga, B, I
n, Fe, Al, Cr) is a compound that converts into an oxide when heated, such as a hydroxide, a carbonate,
Oxalate and nitrate can also be used.
本発明の感ガス素子は、次のような諸特性を示す。The gas-sensitive element of the present invention exhibits the following characteristics.
まず、各種ガスのガス濃度に対する抵抗値変化、すなわ
ち感度特性は、第２図に示すように、たて軸にガスの存
在しない時の基準となる抵抗値Ｒｏとガス雰囲気中の抵
抗値Ｒｇとの比Ｒｏ／Ｒｇをとり、よこ軸にガスの濃度
Ｖｏｌ％をとって曲線化すると、本発明による感ガス素
子は実線で示すように、ガス濃度Ｖｏｌ％が広範囲に変
化しても抵抗値比Ｒｏ／Ｒｇに飽和せずに直線的に変化
する。First, the change in resistance value with respect to the gas concentration of various gases, that is, the sensitivity characteristic, is determined by the resistance value Ro, which is the reference value when no gas is present, on the vertical axis, and the resistance value Rg in the gas atmosphere, as shown in Figure 2. If we take the ratio Ro/Rg and plot the gas concentration Vol% on the horizontal axis to form a curve, we can see that the gas-sensitive element according to the present invention maintains a resistance value ratio even if the gas concentration Vol% changes over a wide range, as shown by the solid line. It changes linearly without being saturated at Ro/Rg.
なお第２図中に従来の感ガス体を用いたものを参考例と
して点線で示すと、その抵抗値変化は本発明のものに比
較し小さ＜、０．１Ｖｏｌ％のガス濃度で飽和してしま
う。In addition, in Fig. 2, a reference example using a conventional gas-sensitive body is shown by a dotted line.The change in resistance value is smaller than that of the present invention, and is saturated at a gas concentration of 0.1 Vol%. Put it away.
特に本発明による感ガス素子は、炭素元素Ｃが２個以上
の炭化水素（Ｃ２Ｈ６，Ｃ３Ｈ８，Ｃ４Ｈ１０・・・）
に対して炭素元素Ｃが多ければ多いほど感度がよくなる
。In particular, the gas-sensitive element according to the present invention uses hydrocarbons containing two or more carbon elements (C2H6, C3H8, C4H10...)
The more carbon element C there is, the better the sensitivity becomes.
このことは本発明の感ガス体は成分分析用の測定装置に
用いれば効果的である。This means that the gas-sensitive body of the present invention is effective when used in a measuring device for component analysis.
本発明感ガス素子の感ガス体の組成比を種々変えた具体
的実施列についてガス濃度０Ｖｏｌ％の時の抵抗値Ｒｏ
および、この抵抗値ＲｏとＣ４Ｈ１０のガス濃度０．１
Ｖｏｌ％の時の抵抗値Ｒｇとの比ＲＲｏ／Ｒｇを示すと
第１表のようになる。Resistance Ro when the gas concentration is 0 Vol.
And this resistance value Ro and the gas concentration of C4H10 0.1
Table 1 shows the ratio RRo/Rg to the resistance value Rg at Vol%.
なお第１表には本発明感ガス素子の感ガス体の組成範囲
を外れるものについても参考例として示した。Table 1 also shows examples of gas-sensitive bodies outside the composition range of the gas-sensitive element of the present invention as reference examples.
本発明の感ガス素子に用いられる感ガス体には、本発明
の効果を害さない範囲で触媒等の副成分を加えることも
できる。The gas-sensitive body used in the gas-sensitive element of the present invention may contain subcomponents such as catalysts within a range that does not impair the effects of the present invention.
例えば、この組成分全体に対し、Ｐｔを１０重量係を越
えないように添加することにより、その感度はさらに向
上する。For example, the sensitivity can be further improved by adding Pt to the entire composition in an amount not exceeding 10 parts by weight.
なおこのＰｔは、Ｈ２ＰｔＣｌ６・Ｈ２Ｏ、ＮＨ４Ｐｔ
Ｃｌ６、Ｋ２ＰｔＣｌ６、ＮａＰｔＣｌなどの化合物と
して添加してもよい。Note that this Pt is H2PtCl6・H2O, NH4Pt
It may also be added as a compound such as Cl6, K2PtCl6, NaPtCl.
第２表は本発明感ガス素子の感ガス体の組成分にｐｔを
添加して製造した場合の各種実施列の抵抗値Ｒｏおよび
抵抗値変化Ｒｏ／Ｒｇを示した。Table 2 shows the resistance value Ro and the resistance value change Ro/Rg of various embodiments when the gas-sensitive element of the present invention was manufactured by adding pt to the composition of the gas-sensitive body.
なお、Ｒｏ，Ｒｇについては前述同様のガス濃度で測定
した値である。Note that Ro and Rg are values measured at the same gas concentration as described above.
本発明の感ガス素子に用いられる感ガス体の組成範囲が
、９９、８５モル％を超えるＺｎＯ，０．１未満のＭｅ
１０２，０．０５モル％未満のＭｅｉ０３であってはガ
スの吸脱による抵抗値変化ＲＯ／Ｒｇが小さく、また２
０モル係未満のＺｎＯ，５０モル係を超えるＭｅ１Ｏ２
，３０モル％を超えるＭｅ２２Ｏ３あるいはこれらに対
して重量比で１０％を超えるｐｔを含有されたものであ
ってはＲｏ／Ｒｇが小さく、さらに抵抗値に対する温度
係数が大きくなり実用的ではなくなる。The composition range of the gas-sensitive body used in the gas-sensitive element of the present invention is 99 to more than 85 mol% ZnO, less than 0.1 mol% Me.
102, Mei03 of less than 0.05 mol% has a small resistance value change RO/Rg due to adsorption and desorption of gas, and 2
ZnO below 0 molar ratio, Me1O2 above 50 molar ratio
, Me22O3 in excess of 30 mol%, or pt in a weight ratio of over 10% with respect to these, Ro/Rg is small and the temperature coefficient relative to the resistance value becomes large, making it impractical.
すなわち９９．８５〜２０モル％，Ｍｅ１０２を０．１
〜５０モル％およびＭｅ２２Ｏ３を０．０５〜３０モル
％を含む組成の焼結体からなる感ガス体でなげれば本発
明の効果は得られない。That is, 99.85 to 20 mol%, Me102 is 0.1
The effect of the present invention cannot be obtained unless the gas-sensitive body is made of a sintered body having a composition containing ~50 mol% and 0.05-30 mol% of Me22O3.
本発明の感ガス素子の温度に対する抵抗値変化は、たと
えば第１表で示した実施例のうち代表して実施列４５に
ついて示すと、第３図のようになり、温度変化に対して
ほぼ一定の抵抗値を呈することがわかる。The change in resistance value with respect to temperature of the gas-sensitive element of the present invention is shown in FIG. 3, for example, for example row 45, which is a representative example among the examples shown in Table 1, and is almost constant with respect to temperature change. It can be seen that the resistance value is .
なお、第３図はたて軸に２０℃の抵抗値Ｒ（２０℃）を
基準とした抵抗変化分△Ｒとの比△Ｒ／Ｒ（２０℃）を
とり、よこ軸に室温付近の温度をとって示してある。In addition, in Figure 3, the vertical axis shows the ratio △R/R (20°C) to the resistance change △R based on the resistance value R (20°C) at 20°C, and the horizontal axis shows the temperature near room temperature. is shown.
さらに本発明の実施列４５および実施例１０５の感ガス
体をヒータ付の感ガス素子として構成した場合に、その
ヒータに印加するヒータ電圧Ｖの変動に対する抵抗値変
化は、第４図に示すように、極めて少ない。Furthermore, when the gas-sensitive bodies of Example 45 and Example 105 of the present invention are configured as gas-sensitive elements with heaters, the resistance value changes with respect to fluctuations in the heater voltage V applied to the heater, as shown in FIG. , extremely few.
応答特性については、第５図に示すようにガス注入から
所定の抵抗値までに１秒以内で到達し、ガス除去後も数
秒以内に無ガス状態時の抵抗値に戻どるなどすぐれた特
性を示す。As for the response characteristics, as shown in Figure 5, the specified resistance value is reached within one second after gas injection, and even after the gas is removed, the resistance value returns to the gas-free state within a few seconds. show.
第１図は本発明の感ガス素子の外観を示す斜視図、第２
図〜第５図は本発明の感ガス素子の諸性能を示す特性図
である。
１・・・・・・感ガス素子、５・・・・・・感ガス体。FIG. 1 is a perspective view showing the appearance of the gas-sensitive element of the present invention, and FIG.
5 to 5 are characteristic diagrams showing various performances of the gas-sensitive element of the present invention. 1... Gas-sensitive element, 5... Gas-sensitive body.
Claims (1)
を具備してなる感ガス素子において、前記感ガス体は、
モル比組成でＺｎＯを９９．８５〜２０％、Ｍｅ１Ｏ２
を０．１〜５０％（ただし、Ｍｅ１はＴｉ，Ｚｒ，Ｈｆ
，Ｓｎ，Ｇｅのうち少なくとも一種）およびＭｅ２２Ｏ
３を０．０５〜３０％（ただし、Ｍｅ２はＧａ，Ｂ，Ｉ
ｎ，Ｆｅ，Ａｌ，Ｃｒのうち少なくとも一種）を含む焼
結体からなることを特徴とする感ガス素子。1. In a gas-sensitive element comprising a pair of electrodes and a gas-sensitive body provided between the electrodes, the gas-sensitive body:
Molar composition of ZnO: 99.85-20%, Me1O2
0.1 to 50% (however, Me1 is Ti, Zr, Hf
, Sn, Ge) and Me22O
3 from 0.05 to 30% (however, Me2 is Ga, B, I
1. A gas-sensitive element comprising a sintered body containing at least one of n, Fe, Al, and Cr.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5596575A JPS589376B2 (en) | 1975-05-14 | 1975-05-14 | gas sensing element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5596575A JPS589376B2 (en) | 1975-05-14 | 1975-05-14 | gas sensing element |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS51132889A JPS51132889A (en) | 1976-11-18 |
| JPS589376B2 true JPS589376B2 (en) | 1983-02-21 |
Family
ID=13013781
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5596575A Expired JPS589376B2 (en) | 1975-05-14 | 1975-05-14 | gas sensing element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS589376B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6346381Y2 (en) * | 1983-06-02 | 1988-12-01 |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3933500B2 (en) * | 2002-03-13 | 2007-06-20 | 新コスモス電機株式会社 | Semiconductor gas detector |
-
1975
- 1975-05-14 JP JP5596575A patent/JPS589376B2/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6346381Y2 (en) * | 1983-06-02 | 1988-12-01 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS51132889A (en) | 1976-11-18 |
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