JPS59105552A - Gas detecting element - Google Patents
Gas detecting elementInfo
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- JPS59105552A JPS59105552A JP21596982A JP21596982A JPS59105552A JP S59105552 A JPS59105552 A JP S59105552A JP 21596982 A JP21596982 A JP 21596982A JP 21596982 A JP21596982 A JP 21596982A JP S59105552 A JPS59105552 A JP S59105552A
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- weight
- added
- gas
- parts
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Classifications
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- 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】
この発明はＳｎＯ２に少量のＰｄを添加したガス検出素
子の改良に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an improvement of a gas detection element in which a small amount of Pd is added to SnO2.
この明細書での用語法として、Ｐｄやｐｔはその金属だ
けでなく酸化物や塩化物等の化合物をも意味するものと
し、その添加量は常に金属Ｐｄや金属Ｐｊに換算した値
をＳｎＯ□１００重量部当りの添加重量部として示すも
のとする。このようにするのはＰｄやＰｔの存在状態が
、素子の使用等によって変化し特定し難いことによる。As used in this specification, Pd and pt refer not only to the metal but also to compounds such as oxides and chlorides, and the amount added is always the value converted to metal Pd or metal Pj by SnO□ It shall be expressed as parts by weight added per 100 parts by weight. This is done because the state of existence of Pd and Pt changes depending on the use of the element and is difficult to specify.
ＳｎＯ２に少量のＰｄを添加した素子は、ＣＨ４やイソ
ブタンへの感度が高く経時的にも安定であるため、広く
用いられている。例えば特公昭５〇−２３ｇ１７号は、
粒径約１μのＳ ｎ ０２に０．８ｗｔ％のＰｃｔを加
えた金属酸化物半導体をガス検出材料とし、これにＳｎ
Ｏ３と等重量のアルミナ骨材を加えシリカゾルをバイン
ダーとして成型した素子を提案し、イソブタンに高感度
で長期間連続して使用しても安定な素子が得られること
を報告している。Elements in which a small amount of Pd is added to SnO2 are widely used because they have high sensitivity to CH4 and isobutane and are stable over time. For example, Special Public Interest Publication No. 50-23g17,
A metal oxide semiconductor made by adding 0.8 wt% Pct to Sn 02 with a particle size of approximately 1 μm was used as a gas detection material, and Sn
We have proposed an element molded by adding alumina aggregate of the same weight as O3 and using silica sol as a binder, and have reported that it is highly sensitive to isobutane and is stable even when used continuously for a long period of time.
しかしこのような素子にも問題が有り、第１に通電再開
直後に素子の抵抗値が異常に低下する時間（以下初期誤
動作時間とする）が長く、第２に放置状態から通電状態
への移行時に素子の抵抗値が１〜３ケ月の間異常な挙動
を示す（以下この現象をレベルシフトとする）。そして
ガス検出装置は初期誤動作によって誤報し、レベルシフ
トによって検出精度が低下する。However, such devices also have problems, firstly, the time it takes for the resistance value of the element to abnormally drop immediately after power is resumed (hereinafter referred to as initial malfunction time) is long, and secondly, the transition from an unattended state to a energized state is long. Sometimes, the resistance value of the element exhibits abnormal behavior for 1 to 3 months (hereinafter, this phenomenon will be referred to as a level shift). Then, the gas detection device gives a false alarm due to initial malfunction, and the detection accuracy decreases due to the level shift.
初期誤動作やレベルシフトは、ＳｎＯ□ｌの素子や、Ｐ
ｔやＡｕ等の助触媒を加えた素子でも生ずる。むしろ実
際には、Ｐｄを加えた素子が最も初期誤動作時間が短く
レベルシフトも小さいのである。そして初期誤動作やレ
ベルシフトに対して、Ｐｄの添加以上に効果のある対策
は発見されていない。Initial malfunctions and level shifts are caused by SnO□l elements and P
This phenomenon also occurs in devices to which a co-catalyst such as T or Au is added. Rather, in reality, the element to which Pd is added has the shortest initial malfunction time and the smallest level shift. No countermeasure has been discovered that is more effective than the addition of Pd against initial malfunctions and level shifts.
この発明は、通電再開直後の初期誤動作を短縮し、レベ
ルシフトを小さくした素子の提供を目的とする。The object of the present invention is to provide an element that reduces the initial malfunction immediately after restarting energization and reduces level shift.
この発明はＰｄとＰｔとの複合効果に着目したもので、
ＳｎＯ□に対して０．１〜０．５重世部のＰｄと０．０
１〜０．０６重量部のＰｔとを併用し、ＰｄとＰｊとの
添加重量の比を１５＝１〜３：１としたことを特徴とす
る。This invention focuses on the combined effect of Pd and Pt,
Pd of 0.1 to 0.5 overlap with SnO□ and 0.0
It is characterized in that 1 to 0.06 parts by weight of Pt is used in combination, and the weight ratio of Pd to Pj is 15=1 to 3:1.
以下にこの発明を実施例に基づいて説明する。The present invention will be explained below based on examples.
ｉｌｌ ガス検出素子の製造例
５ｎＣ１４水溶液をＮＨ３で中和し、ややＮＨ３過剰（
ｐＨ７〜８）で水酸化スズを沈澱させる。水酸化スズの
沈澱に水を加え、遠心分離により沈澱と水とを分離し、
沈澱を洗浄する。ついで水酸化スズを１００°Ｃで１時
間乾燥し、８００’Ｃに空気気流中で３時間加熱し、Ｓ
ｎＯを得る。ill Gas detection element production example 5NC14 aqueous solution was neutralized with NH3, and a slight excess of NH3 (
tin hydroxide is precipitated at pH 7-8). Add water to the tin hydroxide precipitate, separate the precipitate and water by centrifugation,
Wash the precipitate. The tin hydroxide was then dried at 100°C for 1 hour, heated to 800°C in a stream of air for 3 hours, and the S
Obtain nO.
ＳｎＯ□に塩化白金酸と塩化パラジウムとの混合水溶液
を加えてパラジウムや白金を含浸させ、乾燥後７００℃
に１時間加熱し、ＰｔやＰｄを担持させる。ついでＳｎ
Ｏ３と等重量の１０００メツシユのアルミナを混合し、
５ｎｏ２１．００重量部に対して約１重量部の不定形シ
リカゾルをバインダーとし、第１図に示す形状の素子に
成型する。図において（１）は金属酸化物半導体、Ｌ２
Ｌ （３１は使用時に約１．５Ωとなる一対のヒータ兼
用の貴金属電極で、成型はあらかじめ並行に配置した貴
金属電極（２）。Add a mixed aqueous solution of chloroplatinic acid and palladium chloride to SnO□ to impregnate it with palladium and platinum, and dry at 700°C.
The mixture is heated for 1 hour to support Pt and Pd. Then Sn
Mix 1000 mesh of alumina of equal weight with O3,
About 1 part by weight of amorphous silica sol was used as a binder for 1.00 parts by weight of 5no2, and the element was molded into an element having the shape shown in FIG. In the figure, (1) is a metal oxide semiconductor, L2
L (31 is a pair of noble metal electrodes that also serve as a heater and have a resistance of about 1.5Ω when in use, and the noble metal electrodes (2) are molded in advance and arranged in parallel.
（３）に半導体（１）を塗布し、６００°Ｃに１０分加
熱した後、不定形シリカゾルを半導体＋１１に含浸させ
再度７００°Ｃに１０分間加熱することにより行った。Semiconductor (1) was applied to (3), heated at 600°C for 10 minutes, and then semiconductor +11 was impregnated with amorphous silica sol and heated again at 700°C for 10 minutes.
このようにして各組成の素子を３０個ずつ製作する。In this way, 30 elements of each composition are manufactured.
（２）測定回路と測定方法
ガス検出素子（１０）の測定及び通電用回路を第２図に
示す。素子（ｌＯ）の各ヒータ兼用電極＋２１． ！３
＋にそれぞれトランス（１１）を介して０．８ｖ○１ｔ
のヒータ電圧を加え、素子（ｌＯ）を約４００°Ｃに加
熱する。素子（１０）には４にΩの負荷抵抗（１２）を
接続し、トランス（ｌ １）により１０ ｖｏｌｔの回
路電圧を供給し、抵抗（１２）の両端間電圧（ＶＲＬ）
から素子（ｌＯ）の特性を求める。素子（ｌＯ）の加熱
温度を４００°Ｃとしたのは、０．１〜０．５重量部の
Ｐｄを加えた素子に対して最も好ましい結果が得られる
温度だからである。加熱温度を下げるとＣＨ４やイソブ
タンへの相対感度が低下し、Ｈ２やアルコールへの感度
が増す。またガスへの応答速度が低下し、初期誤動作時
間も長くなる。(2) Measuring circuit and measuring method A circuit for measuring and energizing the gas detection element (10) is shown in FIG. Each heater electrode of the element (lO) +21. ! 3
+0.8v○1t via transformer (11) respectively
A heater voltage of 10.degree. C. is applied to heat the element (lO) to about 400.degree. A load resistor (12) of 4Ω is connected to the element (10), a circuit voltage of 10 volts is supplied by the transformer (l1), and the voltage across the resistor (12) (VRL) is
The characteristics of the element (lO) are determined from The heating temperature of the element (lO) was set to 400°C because this is the temperature at which the most favorable results can be obtained for an element to which 0.1 to 0.5 parts by weight of Pd is added. When the heating temperature is lowered, the relative sensitivity to CH4 and isobutane decreases, and the sensitivity to H2 and alcohol increases. Furthermore, the response speed to gas decreases, and the initial malfunction time also increases.
加熱温度を増すと、金属酸化物半導体の熱的劣化が進み
Ｈ２やアルコールへの感度が経時的に増大する。このよ
うな理由で、素子（ｌＯ）の通電温度を４００°Ｃとす
る。When the heating temperature is increased, thermal deterioration of the metal oxide semiconductor progresses, and sensitivity to H2 and alcohol increases over time. For this reason, the current supply temperature of the element (lO) is set to 400°C.
各素子を４００ ’Ｃに１ケ月間通電加熱した後に測定
を開始する。得られた素子３０個のうち１０個を用いて
各種ガスへの感度や応答速度及び素子の抵抗温度係数を
求める。また他の１０個を用いて初期誤動作時間を求め
る。残りの１０個のうち５個を用いてレベルシフトにつ
いて測定し、他の５個を連続通電して比較例とする。ま
たこれらの素子１０個により素子の経時特性を確認する
。測定結果は原則として平均値により表示し、測定雰囲
気は２０℃で湿度６５％とし温度や湿度の影響をさける
。Measurement is started after heating each element to 400'C for one month. Sensitivity to various gases, response speed, and temperature coefficient of resistance of the elements are determined using 10 of the 30 elements obtained. In addition, the initial malfunction time is determined using the other 10 items. Level shift was measured using 5 out of the remaining 10, and the other 5 were continuously energized to serve as a comparative example. Furthermore, the aging characteristics of the elements were confirmed using these 10 elements. In principle, the measurement results are displayed as average values, and the measurement atmosphere is set at 20° C. and 65% humidity to avoid the effects of temperature and humidity.
結果を表にまとめて示す。The results are summarized in a table.
＋３１ Ｐｄの添加効果
Ｐｄの添加は水素やアルコール等の防害ガスへの感度を
抑制し、ＣＨ４やイソブタンへの感度と応答速度とを高
める。この効果は０．１重量部以上の添加で著しく大き
くなる。Ｐｄを０゜５重量部以上添加すると、抵抗温度
係数が増大して電源電圧の変動（ヒータ電圧の変動）に
よる検出誤差が増大する。また長期間連続通電するとＨ
２やアルコールへの感度が増す現象が生じ、素子の信頼
性を損ねる。+31 Effect of addition of Pd Addition of Pd suppresses sensitivity to harmful gases such as hydrogen and alcohol, and increases sensitivity and response speed to CH4 and isobutane. This effect becomes significantly greater when 0.1 part by weight or more is added. When Pd is added in an amount of 0.5 parts by weight or more, the temperature coefficient of resistance increases and detection errors due to fluctuations in power supply voltage (fluctuations in heater voltage) increase. Also, if the current is turned on continuously for a long period of time,
A phenomenon of increased sensitivity to 2 and alcohol occurs, impairing the reliability of the device.
０．１重量部以下のｐｔをＰｄと併用しても（試料Ｎｏ
２〜９）、ガスへの感度と応答速度はあまり変化せ
ず、この添加量の範囲ではガスへの感度と応答速度はＰ
ｄの添加量により定まる。Even if 0.1 parts by weight or less of pt is used in combination with Pd (sample No.
2-9), the sensitivity to gas and the response speed do not change much, and in this range of addition amount, the sensitivity to gas and the response speed are P
It is determined by the amount of d added.
ガスへの感度と応答速度の面から、Ｐｄの添加量を０１
〜０．５重量部とする。From the viewpoint of sensitivity to gas and response speed, the amount of Pd added was set to 0.1
~0.5 parts by weight.
（４）初期誤動作時間
１０日間無通電で放置した素子１０個について、通電開
始後３分程度の挙動を調べる。初期誤動作時間として、
イソブタン５００ ｐｐｍに相当する抵抗値まで素子の
抵抗値が回復するのに要する時間を示す。(4) Initial malfunction time: The behavior of the 10 elements left without energization for 10 days is examined for about 3 minutes after the start of energization. As the initial malfunction time,
It shows the time required for the resistance value of the element to recover to the resistance value corresponding to 500 ppm of isobutane.
初期誤動作は少量のＰｔ添加により著しく短縮し、試料
ＮＯ［１ｊのｐｔ無添加の素子では第３図の破線の）の
ように約９０秒の初期誤動作時間を要するのに対して、
０．０３重量部のＰｔを併用した素子（試料Ｎｏ （４
） ）では約３０秒に過ぎない（第３図実線（Ａ））。The initial malfunction time is significantly shortened by the addition of a small amount of Pt, whereas it takes about 90 seconds for the initial malfunction time as in sample No. 1j (indicated by the broken line in Fig. 3 for the element without pt addition).
Element using 0.03 parts by weight of Pt (sample No. (4)
)), it takes only about 30 seconds (solid line (A) in Figure 3).
Ｐｔの添加効果はＰｔとＰｄとの添加量の比によって定
まり、Ｐｔの添加量が小さい場合Ｐｄの添加量を増すと
効果が失なわれてしまう（試料３と試料８）。またＰｔ
添加量が大きい場合は、Ｐｄ添加量を減少させても失な
われてしまう（試料５と試料７）。良い結果が得られる
のはＰｔ／Ｐｄの比がＩ／１５〜１／３の範囲に限られ
る（試料３〜５及び試料９）。The effect of adding Pt is determined by the ratio of the amounts of Pt and Pd added, and when the amount of Pt added is small, the effect is lost when the amount of Pd added is increased (Samples 3 and 8). Also Pt
If the amount added is large, Pd will be lost even if the amount added is reduced (Samples 5 and 7). Good results are obtained only when the Pt/Pd ratio is in the range of I/15 to 1/3 (Samples 3 to 5 and Sample 9).
（５） レベルシフト
３ｊ月間無通電放置した素子の、通電再開直後の挙動を
第４図に示す。実線（ト）は試料Ｎｏ ｆ４１のＰｊを
併用した素子の結果を示し、破線（１３）は試料Ｎ０（
１）のＰｔ無添加の素子の特性を示す。なお結果はイソ
ブタン８０００ ｐｐｍに対する素子５個の抵抗値の平
均を示すものである。いずれの場合も、最初素子の抵抗
値は異常に低下し、その後かなり高抵抗化した後に２週
間から２ｊ月程度で安定する。(5) Level Shift 3j Figure 4 shows the behavior of an element that has been left without energization for a month immediately after energization is resumed. The solid line (g) shows the results of the element using sample No f41 in combination with Pj, and the broken line (13) shows the result of the element using sample No f41 (
1) The characteristics of the Pt-free element are shown. Note that the results show the average resistance value of five elements with respect to 8000 ppm of isobutane. In either case, the resistance value of the element first drops abnormally, then increases to a considerably high resistance value, and then stabilizes in about 2 weeks to 2 months.
この現象をレベルシフトとすると、レベルシフトによる
変化は素子の抵抗値として最大で約３０％、検出ガス濃
度として約６０％になる。しかしレベルシフトは素子の
不可逆劣化を意味するものではなく、レベルシフト終了
後の素子の抵抗後は無通電放置に移す前の値に一致する
。従ってレベルシフトは長期間無通電状態におくことに
よって生ずる一種のヒステリシ子現象である。If this phenomenon is referred to as a level shift, the change due to the level shift will be approximately 30% at maximum in the resistance value of the element and approximately 60% in the detected gas concentration. However, the level shift does not mean irreversible deterioration of the element, and the resistance of the element after the level shift is equal to the value before being left unenergized. Therefore, the level shift is a type of hysteresis phenomenon caused by leaving the device in a non-energized state for a long period of time.
第４図の実線＜Ａ）と破線（Ｂ）とを比較すると、Ｐｔ
の併用（実線（８））によりレベルシフトの完了に要す
る期間は著しく短縮される。レベルシフトに対してＰｊ
が有効な範囲は、初期誤動作の場合と同様に、ＰｔとＰ
ｄとの添加比によって定まり、Ｐｔ／Ｐｄの比が１／１
５〜１／３が望ましい。Ｐｊの添加量よりもｐｔとＰｄ
の比により効果が生ずることは、添加したＰｊとＰｄと
の間に強い複合関係があることを示唆する。本発明では
ＰｔとＰｄの複合効果の面から、Ｐｊ ： Ｐｄの比を
１：１５〜１；３とする。なおＰｔを０．０１重量部と
Ｐｄを０．２５重量部加えた素子（試料（２））で良い
結果が得られなかったことからＰｔ添加量の下限を０．
０１重量部とした。Comparing the solid line <A) and the broken line (B) in Fig. 4, it is found that Pt
By using the combination (solid line (8)), the period required to complete the level shift is significantly shortened. Pj for level shift
As in the case of initial malfunction, the valid range is Pt and P
It is determined by the addition ratio with d, and the Pt/Pd ratio is 1/1.
5 to 1/3 is desirable. pt and Pd than the addition amount of Pj
The fact that the effect occurs depending on the ratio of Pj and Pd suggests that there is a strong complex relationship between the added Pj and Pd. In the present invention, from the viewpoint of the combined effect of Pt and Pd, the ratio of Pj:Pd is set to 1:15 to 1:3. Note that good results were not obtained with the element (sample (2)) in which 0.01 part by weight of Pt and 0.25 part by weight of Pd were added, so the lower limit of the amount of Pt added was set at 0.01 parts by weight.
01 parts by weight.
（６）抵抗温度係数
素子の抵抗温度係数は、００６重量部以上のＰｊの添加
により正から負に変化する。Ｐｄ量を０．２５重量部と
した際の結果を第５図に示すが、Ｐｊ量が０．０３〜０
．０５重量部では正の抵抗温度係数が得られるのに対し
、０．０７重量部では負の値となる。(6) Temperature Coefficient of Resistance The temperature coefficient of resistance of the element changes from positive to negative by adding 006 parts by weight or more of Pj. The results when the Pd amount is 0.25 parts by weight are shown in FIG. 5, but when the Pj amount is 0.03 to 0.
．． At 0.05 parts by weight, a positive temperature coefficient of resistance is obtained, whereas at 0.07 parts by weight, a negative value is obtained.
なお図の横軸は素子の温度及びそれに対応する電源電圧
を示すものである。Note that the horizontal axis in the figure indicates the temperature of the element and the corresponding power supply voltage.
抵抗温度係数が負になると、回路電圧の変動と素子の温
度変化とが相乗して、大きな検出誤差を生むことになる
。また回路電圧を高め回路電流による自己発熱を大きく
した素子では、抵抗値の変化が自己発熱量の変化を増幅
し、検出精度が低下するとともにヒステリシスを大きく
することになる。この理由で抵抗温度係数は正であるこ
とが望ましく、Ｐｔの添加量を０．０６重量部以下とし
た。When the temperature coefficient of resistance becomes negative, fluctuations in circuit voltage and changes in element temperature combine to produce a large detection error. In addition, in an element in which the circuit voltage is increased and the self-heating due to the circuit current is increased, a change in resistance value amplifies a change in the amount of self-heating, resulting in a decrease in detection accuracy and an increase in hysteresis. For this reason, it is desirable that the temperature coefficient of resistance is positive, and the amount of Pt added is 0.06 parts by weight or less.
以上に説明したようにこの発明は、少量のＰｔをＰｄと
併用することにより、初期誤動作を短縮するとともに、
無通電から通電への移行によるレベルシフト期間を短縮
し、ガス検出素子の信頼性を高めるものである。As explained above, this invention reduces initial malfunction by using a small amount of Pt in combination with Pd, and
This shortens the level shift period caused by the transition from non-energization to energization, thereby increasing the reliability of the gas detection element.
第１図はガス検出回路の１例を示す断面図、第２図はガ
ス検出回路の回路図、第３図は素子の初期誤動作を示す
特性図、第４図は素子のレベルシフトを示す特性図、第
５図は素子の抵抗温度依存性を示す特性図である。
（１）：金属酸化物半導体、
＋２＋、 ＋３） ；ヒータ兼用電極、（１０） ；ガ
ス検出素子、 （＋２） ；負荷抵抗。
特許出願人 フイガロ技研株式会社
（１２） ２８を第１図
第２図Fig. 1 is a cross-sectional view showing an example of a gas detection circuit, Fig. 2 is a circuit diagram of the gas detection circuit, Fig. 3 is a characteristic diagram showing initial malfunction of the element, and Fig. 4 is a characteristic showing level shift of the element. FIG. 5 is a characteristic diagram showing the resistance temperature dependence of the element. (1): metal oxide semiconductor, +2+, +3); heater electrode, (10); gas detection element, (+2); load resistance. Patent applicant Figaro Giken Co., Ltd. (12) 28 in Figure 1 Figure 2
Claims (1)
Ｐｄを添加し、これに一対の電極を接続した素子におい
て、 前記酸化第二錫にはＰｄに加えてＰｊを添加し、かつＰ
ｊの添加量は酸化第二錫１００重量部に対して０．０１
〜０．０６重量部で、ＰｄとＰｊの添加重量の比は１５
：１〜３二ｌであることを特徴とするガス検出素子。(1) In an element in which 0.1 to 0.5 parts by weight of Pd is added to 100 parts by weight of stannic oxide, and a pair of electrodes are connected to this, Pj is added to the stannic oxide in addition to Pd. , and P
The amount of j added is 0.01 per 100 parts by weight of stannic oxide.
~0.06 parts by weight, the ratio of the added weight of Pd and Pj is 15
A gas detection element characterized in that: 1 to 32 l.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21596982A JPS59105552A (en) | 1982-12-09 | 1982-12-09 | Gas detecting element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21596982A JPS59105552A (en) | 1982-12-09 | 1982-12-09 | Gas detecting element |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59105552A true JPS59105552A (en) | 1984-06-18 |
| JPH0225455B2 JPH0225455B2 (en) | 1990-06-04 |
Family
ID=16681233
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21596982A Granted JPS59105552A (en) | 1982-12-09 | 1982-12-09 | Gas detecting element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59105552A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010145382A (en) * | 2008-12-22 | 2010-07-01 | Toyama Prefecture | GAS SENSOR FOR DETECTING Total-VOC, AND METHOD FOR MANUFACTURING THE SAME |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0340973U (en) * | 1989-08-30 | 1991-04-19 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS556188A (en) * | 1978-06-22 | 1980-01-17 | Westinghouse Electric Corp | Module type shell and tube heat exchanger |
| JPS55136947A (en) * | 1979-04-13 | 1980-10-25 | Matsushita Electric Works Ltd | Gas detecting element |
| JPS5773661A (en) * | 1980-10-25 | 1982-05-08 | Matsushita Electric Works Ltd | Sensing element for combustible gas |
-
1982
- 1982-12-09 JP JP21596982A patent/JPS59105552A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS556188A (en) * | 1978-06-22 | 1980-01-17 | Westinghouse Electric Corp | Module type shell and tube heat exchanger |
| JPS55136947A (en) * | 1979-04-13 | 1980-10-25 | Matsushita Electric Works Ltd | Gas detecting element |
| JPS5773661A (en) * | 1980-10-25 | 1982-05-08 | Matsushita Electric Works Ltd | Sensing element for combustible gas |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010145382A (en) * | 2008-12-22 | 2010-07-01 | Toyama Prefecture | GAS SENSOR FOR DETECTING Total-VOC, AND METHOD FOR MANUFACTURING THE SAME |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0225455B2 (en) | 1990-06-04 |
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