JP2002168832A - Gas detecting method and gas-concentration measuring method as well as gas sensor - Google Patents
Gas detecting method and gas-concentration measuring method as well as gas sensorInfo
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- JP2002168832A JP2002168832A JP2000366136A JP2000366136A JP2002168832A JP 2002168832 A JP2002168832 A JP 2002168832A JP 2000366136 A JP2000366136 A JP 2000366136A JP 2000366136 A JP2000366136 A JP 2000366136A JP 2002168832 A JP2002168832 A JP 2002168832A
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- gas
- measured
- specific component
- discharge
- concentration
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明はガス検知方法及びガ
ス濃度測定方法並びにガスセンサに関する。更に詳しく
は、新規なガスの検知及び濃度測定方法であり、新規な
ガスセンサに関し、被測定ガスの組成、及び被測定ガス
中に含まれる測定対象ガスの種類によって各々固有であ
る放電特性を利用するガス検知方法、ガス濃度測定方法
及びガスセンサに関する。本発明のガスセンサは、あら
ゆる被測定ガスの検知及び定量に用いることができる。The present invention relates to a gas detection method, a gas concentration measurement method, and a gas sensor. More specifically, the present invention relates to a novel gas detection and concentration measurement method, and relates to a novel gas sensor, using a discharge characteristic that is unique to each of the composition of the gas to be measured and the type of the gas to be measured contained in the gas to be measured. The present invention relates to a gas detection method, a gas concentration measurement method, and a gas sensor. The gas sensor of the present invention can be used for detecting and quantifying any gas to be measured.
【０００２】[0002]
【従来の技術】従来のガスの検知方法及び濃度測定方法
としては、（１）測定対象である成分ガスの接触により
抵抗値が変化する特性を用いる方法や、（２）固体電解
質体中におけるイオン伝導性を用いる方法等が知られて
いる。2. Description of the Related Art Conventional gas detection methods and concentration measurement methods include (1) a method using a characteristic in which a resistance value changes due to contact with a component gas to be measured, and (2) an ion in a solid electrolyte body. Methods using conductivity and the like are known.
【０００３】[0003]
【発明が解決しようとする課題】しかし、（１）の方法
では主に可燃性の成分ガスしか検知・定量することがで
きない。また、（２）では固体電解質体内でイオン伝導
できるイオンを生成できる成分ガスしか検知・定量する
ことができない。このように限られた種類の成分ガスし
か検知・定量することができないという問題がある。ま
た、例えば、（２）の方法では固体電解質体が活性化さ
れる温度である約５００℃以上においてしか検知・定量
が行えない等、特殊な温度及び圧力等の条件を整えなけ
れば測定を行うことができないという問題がある。However, in the method (1), only the flammable component gas can be detected and quantified. In (2), only a component gas capable of generating ions capable of conducting ions in the solid electrolyte can be detected and quantified. Thus, there is a problem that only limited types of component gases can be detected and quantified. Further, for example, in the method (2), measurement and measurement are performed unless special conditions such as temperature and pressure are established, such that detection and quantification can be performed only at about 500 ° C. or more, which is the temperature at which the solid electrolyte body is activated. There is a problem that you can not.
【０００４】本発明は上記問題点を解決するものであ
り、極めて多種の成分ガスの検知・定量を行うことがで
き、更には、幅広い測定条件（測定温度及び測定圧力
等）において検知・定量を行うことができるガス検知方
法、ガス濃度測定方法及びガスセンサを提供することを
目的とする。The present invention has been made to solve the above problems, and can detect and quantify extremely various kinds of component gases. Further, the present invention can detect and quantify a wide range of measurement conditions (measurement temperature and measurement pressure, etc.). It is an object to provide a gas detection method, a gas concentration measurement method, and a gas sensor that can be performed.
【０００５】[0005]
【課題を解決するための手段】単一の成分ガスを電極対
間において放電させる場合の放電破壊電圧と放電維持電
圧とは、成分ガスの種類及び使用する電極材料等によっ
て特異な値となることが知られている。本発明者らはこ
の事実に基づき、混合ガスにおいてもその組成によって
放電破壊電圧及び放電維持電圧は各々特異な値であるこ
とを見出した。更に、放電させる電極の構成材料及びそ
の組み合わせによっても放電破壊電圧又は放電維持電圧
は特異な値を示すことを見出した。これらの特性を利用
して特定の成分ガスを含有する場合に放電破壊電圧及び
放電維持電圧の少なくとも一方が特異的に変化する電極
材料及び電極材料の組み合わせを選択して使用すること
で、放電特性からこの成分ガスが含有されているか否か
を知ることができることを見出し、本発明を完成させ
た。また、被測定ガスを電極対間で放電させた場合の放
電電流値は、含有される成分ガスの濃度に相関すること
を利用し、混合ガス中の成分ガスの濃度を測定できるこ
とを見出し、本発明を完成させた。The discharge breakdown voltage and discharge sustaining voltage when a single component gas is discharged between an electrode pair have specific values depending on the type of component gas, the electrode material used, and the like. It has been known. Based on this fact, the present inventors have found that the breakdown voltage and the sustaining voltage of the mixed gas are peculiar values depending on the composition thereof. Furthermore, it has been found that the discharge breakdown voltage or the discharge sustaining voltage shows a unique value depending on the constituent materials of the electrodes to be discharged and the combination thereof. By utilizing these characteristics and selecting and using an electrode material and a combination of electrode materials in which at least one of the discharge breakdown voltage and the discharge sustaining voltage specifically changes when a specific component gas is contained, the discharge characteristics are improved. From this, it was found that it was possible to know whether or not this component gas was contained, and the present invention was completed. Also, the present inventors have found that the discharge current value when the gas to be measured is discharged between the electrode pair can be used to measure the concentration of the component gas in the mixed gas by utilizing the correlation with the concentration of the contained component gas. Completed the invention.
【０００６】本第１発明のガス検知方法は、電極対間に
て被測定ガスを放電させた場合の放電破壊電圧及び放電
維持電圧の少なくとも一方が、該被測定ガス中の特定成
分の有無により変化する特性を有する該電極対を用い
て、該被測定ガスを放電させて放電破壊電圧及び放電維
持電圧の少なくとも一方を測定し、該特性により該被測
定ガス中の上記特定成分の有無を判定することを特徴と
する。In the gas detection method according to the first aspect of the present invention, at least one of the discharge breakdown voltage and the discharge sustaining voltage when the gas to be measured is discharged between the electrode pair is determined by the presence or absence of a specific component in the gas to be measured. Using the electrode pair having changing characteristics, the measurement gas is discharged to measure at least one of a discharge breakdown voltage and a discharge sustaining voltage, and the presence or absence of the specific component in the measurement gas is determined based on the characteristics. It is characterized by doing.
【０００７】上記「被測定ガス」は検知に供される気体
である。この被測定ガスは単一の成分ガスであっても、
また、複数種の成分ガスが混合された混合ガスであって
もよい。また、上記「特定成分」とは測定対象である単
一の成分ガスを意味する。The above-mentioned "gas to be measured" is a gas used for detection. Even if this measured gas is a single component gas,
Further, a mixed gas in which a plurality of types of component gases are mixed may be used. The “specific component” means a single component gas to be measured.
【０００８】上記「放電」はコロナ放電、グロー放電及
びアーク放電の何れであってもよい。但し、放電維持電
圧を測定する場合は放電維持電圧が最も安定しているた
めグロー放電を用いることが好ましい。また、グロー放
電であれば電極の消耗は少ないため好ましい。また、電
極に印加する電圧の波形は、放電破壊電圧及び放電維持
電圧の一方のみの値を測定する場合は特に限定されな
い。一方、放電破壊電圧及び放電維持電圧の両方を測定
する場合は、正弦波、矩形波、三角波及びのこぎり波等
を印加することが好ましい。このような波形の電圧を印
加することにより放電破壊電圧と放電維持電圧とを区別
することができる。The "discharge" may be any of corona discharge, glow discharge and arc discharge. However, when measuring the sustaining voltage, it is preferable to use glow discharge because the sustaining voltage is the most stable. Further, glow discharge is preferable because the consumption of the electrode is small. The waveform of the voltage applied to the electrode is not particularly limited when only one of the discharge breakdown voltage and the discharge sustaining voltage is measured. On the other hand, when measuring both the breakdown voltage and the sustaining voltage, it is preferable to apply a sine wave, a rectangular wave, a triangular wave, a sawtooth wave, or the like. By applying a voltage having such a waveform, the discharge breakdown voltage and the sustaining voltage can be distinguished.
【０００９】上記「放電破壊電圧」は、グロー放電に移
行する直前における最も高い電圧であり、上記「放電維
持電圧」は、コロナ電圧、グロー電圧及びアーク電圧の
いずれであってもよいが、上記のように放電破壊電圧と
放電維持電圧の両方を測定する場合は、グロー電圧であ
ることが好ましい。The "discharge breakdown voltage" is the highest voltage immediately before shifting to glow discharge. The "discharge sustaining voltage" may be any of a corona voltage, a glow voltage and an arc voltage. When both the discharge breakdown voltage and the discharge sustaining voltage are measured as described above, the glow voltage is preferably used.
【００１０】上記「特性」において、被測定ガス中に特
定成分を含有しない場合の放電破壊電圧と特定成分を含
有する場合の放電破壊電圧とは少なくとも１％以上（好
ましくは１０％以上、更に好ましくは１５％以上）の差
異を生じることが好ましい。同様に、放電維持電圧にお
いても少なくとも１％以上（好ましくは１０％以上、更
に好ましくは１５％以上）の差異を生じることが好まし
い。この各々の電圧差が１％未満であるといずれにおい
ても特定成分の検知が困難になる傾向にある。尚、以下
においては、放電破壊電圧に対するこのような特性を
「放電破壊電圧に対する感応性」といい、放電維持電圧
に対するこのような特性を「放電維持電圧に対する感応
性」といい、これらを合わせていうときは単に「電圧に
対する感応性」という。In the above "characteristics", the discharge breakdown voltage when the gas to be measured does not contain a specific component and the discharge breakdown voltage when the gas to be measured contains a specific component are at least 1% or more (preferably 10% or more, more preferably 10% or more). Preferably 15% or more). Similarly, it is preferable that a difference of at least 1% or more (preferably 10% or more, more preferably 15% or more) occurs in the discharge sustaining voltage. If the respective voltage differences are less than 1%, the detection of the specific component tends to be difficult in any case. In the following, such a characteristic with respect to a discharge breakdown voltage is referred to as “sensitivity to a discharge breakdown voltage”, and such a characteristic with respect to a discharge sustaining voltage is referred to as “sensitivity to a discharge sustaining voltage”. Sometimes it is simply referred to as "voltage sensitivity".
【００１１】上記「電極対」は対向する２つの電極から
なる。各々の電極は同じ材料から構成されていてもよ
く、また、異なる材料から構成されていてもよい。電極
を構成する材料は熱伝導率が高いものが好ましい。この
ような材料としては銅（Ｃｕ）、ニッケル（Ｎｉ）及び
白金（Ｒｔ）等を挙げることができる。これらは単体で
用いても、合金等で用いてもよい。このような材料を用
いることにより耐久性の高い電極を得ることができる。The above "electrode pair" is composed of two opposing electrodes. Each electrode may be made of the same material, or may be made of different materials. The material constituting the electrode preferably has a high thermal conductivity. Examples of such a material include copper (Cu), nickel (Ni), and platinum (Rt). These may be used alone or as an alloy. By using such a material, a highly durable electrode can be obtained.
【００１２】また、電極対は、１種の特定成分の有無を
判定するためには、この特定成分の電圧に対する感応性
を有する１種の電極対を１対のみ用いればよいが、この
特定成分の電圧に対する感応性を有する１種の電極対を
２対以上用いてもよい。更に、１種の特定成分の電圧に
対する感応性を有する２種以上の電極対を用いてもよ
い。１種のみの特定成分の電圧に対する感応性を有する
電極を用いる場合は、単一の成分ガスからなる被測定ガ
スが検知対象の特定成分であるか否かを判定することが
できる。In order to determine the presence or absence of one specific component, only one electrode pair having sensitivity to the voltage of the specific component may be used. Two or more electrode pairs having the sensitivity to the above voltage may be used. Further, two or more electrode pairs having sensitivity to the voltage of one specific component may be used. When an electrode having sensitivity to the voltage of only one specific component is used, it can be determined whether or not the gas to be measured consisting of a single component gas is the specific component to be detected.
【００１３】また、特に第２発明のように、２種以上の
特定成分の電圧の各々に対する感応性を有する、２種以
上の電極対を用いることで、複数種の特定成分の有無を
判定することができる。第２発明においても、第１発明
におけると同様に、１種の特定成分の電圧に対する感応
性を有する１種の電極対は１対のみを用いればよいが、
この電極対を２対以上用いてもよい。更に、１種の特定
成分の電圧に対する感応性を有する電極対を２種以上用
いてもよい。Also, as in the second invention, the presence or absence of a plurality of types of specific components is determined by using two or more types of electrode pairs having sensitivity to each of voltages of two or more types of specific components. be able to. In the second invention, as in the first invention, only one electrode pair having sensitivity to the voltage of one specific component may be used.
Two or more electrode pairs may be used. Further, two or more electrode pairs having sensitivity to the voltage of one specific component may be used.
【００１４】第１発明及び第２発明における上記「特定
成分の有無の判定」においては、用いる電極が放電破壊
電圧に対する感応性を有する電極である場合は、この電
極間において被測定ガスを放電させた時の放電破壊電圧
を測定し、この放電破壊電圧が予め得られている特定成
分が含有されない擬似被測定ガスの放電破壊電圧に比べ
て差異を生じる場合に特定成分が含有されているものと
判定することができる。一方、測定された放電破壊電圧
が、予め得られている特定成分が含有されない擬似被測
定ガスの放電破壊電圧とほぼ同じ（差が±５％以内、更
には差が±１％以内）場合は特定成分は含有されていな
いものと判定することができる。これと同様にして、放
電維持電圧に対する感応性を有する電極を用いる場合
も、放電維持電圧の測定により特定成分の有無を判定す
ることができる。尚、擬似被測定ガスとは、特定成分を
除く全ての組成が同じである混合ガスであってもよく、
実際に測定に供される被測定ガス中において特定成分の
電圧に対する感応性に影響しない成分ガスは除いた混合
ガスであってもよい。In the above "determination of the presence or absence of a specific component" in the first invention and the second invention, when the electrode to be used is an electrode having sensitivity to a discharge breakdown voltage, the gas to be measured is discharged between the electrodes. The discharge breakdown voltage at the time of the measurement is measured, and when the discharge breakdown voltage is different from the discharge breakdown voltage of the pseudo measured gas that does not contain the previously obtained specific component, the specific component is included. Can be determined. On the other hand, when the measured discharge breakdown voltage is almost the same as the previously obtained discharge breakdown voltage of the pseudo measured gas containing no specific component (the difference is within ± 5%, and further, the difference is within ± 1%), It can be determined that the specific component is not contained. Similarly, when an electrode having sensitivity to the sustaining voltage is used, the presence or absence of a specific component can be determined by measuring the sustaining voltage. The pseudo measured gas may be a mixed gas having the same composition except for a specific component,
The mixed gas may be a gas from which a component gas that does not affect the sensitivity of a specific component to a voltage is removed from the gas to be measured actually used for measurement.
【００１５】また、第１発明及び第２発明のガス検知方
法は、放電現象を利用するものであり、放電させること
ができる空間と電極さえあれば、温度、雰囲気の圧力等
は特に限定されない。例えば、温度−１０〜５０℃程度
において９０〜１１０ＭＰａにおいて測定することがで
きる。但し、被測定ガスを放電させる時の圧力は放電破
壊電圧及び放電維持電圧に影響する場合もある。このよ
うな場合は圧力変動が小さくなるような装置を用いた
り、放電破壊電圧及び／又は放電維持電圧の測定時の測
定雰囲気下の圧力を知る必要がある。The gas detecting methods of the first and second aspects of the present invention utilize a discharge phenomenon, and the temperature, the pressure of the atmosphere, and the like are not particularly limited as long as there is only a space and an electrode capable of discharging. For example, it can be measured at a temperature of about −10 to 50 ° C. and 90 to 110 MPa. However, the pressure at which the gas to be measured is discharged may affect the discharge breakdown voltage and the discharge sustaining voltage. In such a case, it is necessary to use a device that reduces the pressure fluctuation, or to know the pressure in the measurement atmosphere when measuring the discharge breakdown voltage and / or the discharge sustaining voltage.
【００１６】第３発明のガス濃度測定方法は、電極対間
にて被測定ガスを放電させた場合の放電電流値と、該被
測定ガス中に含まれる特定成分の濃度とが相関する特性
を有する該電極対を用いて、該被測定ガスを放電させて
放電電流値を測定し、該特性により該被測定ガス中の上
記特定成分の濃度を測定することを特徴とする。According to a third aspect of the present invention, there is provided a method for measuring a gas concentration, wherein a characteristic in which a discharge current value when a gas to be measured is discharged between an electrode pair and a concentration of a specific component contained in the gas to be measured is correlated. The measurement gas is discharged by discharging the gas to be measured using the pair of electrodes having the electrode pair, and the concentration of the specific component in the gas to be measured is measured based on the characteristic.
【００１７】上記「被測定ガス」は濃度測定に供される
気体であること以外は、第１発明におけると同様であ
る。上記「特定成分」も第１発明と同様に、測定対象で
ある単一の成分ガスである。また、上記「放電」は第１
発明におけると同様であるが、第３発明においては、放
電時の電流値である上記「放電電流値」を測定するた
め、特にグロー放電を用いることが好ましい。更に、電
極に印加する電圧の波形は特に限定されない。The "measured gas" is the same as in the first invention except that the gas to be measured is a gas used for concentration measurement. The "specific component" is also a single component gas to be measured, as in the first invention. The above “discharge” is the first
Although the same as in the invention, in the third invention, it is particularly preferable to use glow discharge in order to measure the above-mentioned “discharge current value” which is the current value at the time of discharge. Further, the waveform of the voltage applied to the electrode is not particularly limited.
【００１８】上記「特性」における、放電電流値と特定
成分の濃度との相関は正の関数又は負の関数である。
尚、以下においては、放電電流値に対するこのような特
性を「放電電流値に対する感応性」という。In the "characteristics", the correlation between the discharge current value and the concentration of the specific component is a positive function or a negative function.
In the following, such a characteristic with respect to the discharge current value is referred to as “sensitivity to the discharge current value”.
【００１９】上記「電極対」は第１発明におけると同様
に、対向する２つの電極からなる。各々の電極は同じ材
料から構成されていてもよく、また、異なる材料から構
成されていてもよい。電極を構成する材料は高い導電
性、高い融点及び高い熱伝導率の少なくともいずれかの
特性を有する材料を用いることが好ましい。このような
材料としては、白金族（Ｒｕ、Ｒｈ、Ｐｄ、Ｏｓ、Ｉｒ
及びＰｔ）、Ｎｉ及びＣｕ等の少なくとも１種を用いる
ことができる。このような材料を用いることにより安定
した電流を得ることができ、更には耐久性も高い。The "electrode pair" is composed of two opposing electrodes, as in the first invention. Each electrode may be made of the same material, or may be made of different materials. It is preferable to use a material having at least one of high conductivity, high melting point, and high thermal conductivity as a material forming the electrode. Such materials include platinum group (Ru, Rh, Pd, Os, Ir)
And at least one of Pt), Ni and Cu. By using such a material, a stable current can be obtained and the durability is high.
【００２０】また、電極対は、１種の特定成分の濃度を
測定するためには、この特定成分の放電電流値に感応性
を有する１種の電極対を１対のみ用いればよいが、この
１種の特定成分の放電電流値に対する感応性を有する１
種の電極対を２対以上用いてもよい。更に、１種の特定
成分の放電電流値に感応性を有する２種以上の電極対を
用いてもよい。１種の特定成分の放電電流値に対する感
応性のみを有する電極を用いる場合は、単一の成分ガス
からなる被測定ガスが検知対象の特定成分である否かを
判定することができる。In order to measure the concentration of one specific component, only one pair of electrode pairs sensitive to the discharge current value of this specific component may be used. 1 sensitive to the discharge current value of one specific component
Two or more kinds of electrode pairs may be used. Further, two or more electrode pairs sensitive to the discharge current value of one specific component may be used. When an electrode having only one type of sensitivity to the discharge current value of a specific component is used, it is possible to determine whether or not the gas to be measured consisting of a single component gas is the specific component to be detected.
【００２１】また、特に第４発明のように、２種以上の
特定成分の各々の放電電流値に対する感応性を有する２
種以上の電極対を用いることで、複数種の特定成分の濃
度を測定することができる。第４発明においても、第３
発明におけると同様に、１種の特定成分の放電電流値に
対して感応性を有する１種の電極対は１対のみを用いれ
ばよいが、この電極対を２対以上用いてもよい。更に、
１種の特定成分の放電電流値に対して感応性を有する電
極対を２種以上用いてもよい。In addition, as in the fourth aspect of the invention, two or more specific components having sensitivity to the discharge current value of each of the two or more specific components are used.
By using more than one kind of electrode pair, the concentration of a plurality of kinds of specific components can be measured. Also in the fourth invention, the third
As in the present invention, only one electrode pair having sensitivity to the discharge current value of one specific component may be used, but two or more electrode pairs may be used. Furthermore,
Two or more electrode pairs having sensitivity to the discharge current value of one specific component may be used.
【００２２】第３発明及び第４発明において特定成分の
濃度の測定は、以下の様にして行うことができる。例え
ば、放電電流値に対する感応性を有する電極間におい
て、特定成分の濃度を変化させた擬似被測定ガスを放電
させて、特定成分の各濃度における放電電流値を測定す
る。これにより、特定成分の濃度と放電電流値との相関
が得られる。その後、被測定ガスの放電電流値を測定
し、上記の相関に照らし合わせて、特定成分濃度を算出
する。特に、第４発明のように２種以上の特定成分の濃
度を測定する場合は、上記と同様にして、予めこれら各
々の特定成分を含有する擬似被測定ガスの放電電流値
と、各特定成分の濃度との相関を得ておき、この相関に
照らし合わせて被測定ガス中の特定成分の濃度を算出す
る。尚、擬似被測定ガスとは、特定成分を除く全ての組
成が同じである混合ガスであってもよく、実際に測定に
供される被測定ガス中における放電電流値に対する感応
性に影響しない成分ガスは除いた混合ガスであってもよ
い。In the third and fourth inventions, the concentration of the specific component can be measured as follows. For example, a pseudo target gas having a specific component concentration changed is discharged between electrodes having sensitivity to a discharge current value, and a discharge current value at each concentration of the specific component is measured. Thereby, a correlation between the concentration of the specific component and the discharge current value is obtained. Thereafter, the discharge current value of the gas to be measured is measured, and the specific component concentration is calculated in light of the above correlation. In particular, when measuring the concentrations of two or more specific components as in the fourth invention, in the same manner as described above, the discharge current value of the pseudo measured gas containing each of these specific components and the specific component Is obtained in advance, and the concentration of the specific component in the gas to be measured is calculated in light of the correlation. Note that the pseudo measured gas may be a mixed gas having the same composition except for a specific component, and may be a component that does not affect the sensitivity to the discharge current value in the measured gas that is actually used for measurement. The gas may be a mixed gas excluding the gas.
【００２３】更に、第１発明の被測定ガス中の特定成分
の有無を判定するガス検知方法と、第３発明の被測定ガ
ス中の特定成分の濃度を測定する濃度測定方法とを併せ
ることにより、ガスの検知及び濃度測定の両方を行うこ
とができる。即ち、電極対間にて被測定ガスを放電させ
た場合の放電破壊電圧及び放電維持電圧の少なくとも一
方が、該被測定ガスに特定成分が含有されない場合に比
べて該特定成分が含有される場合に高くなる第１特性
と、該電極対間で該被測定ガスを放電させた時の放電電
流値と、該被測定ガス中に含まれる該特定成分の濃度と
が相関する第２特性とを有する該電極対を用いて、該被
測定ガスを放電させて放電破壊電圧及び放電維持電圧の
少なくとも一方と、放電電流値とを測定し、該第１特性
により該被測定ガス中の上記特定成分の有無を判定し、
該第２特性により該被測定ガス中の上記特定成分の濃度
を測定することができる。Further, the gas detecting method of the first invention for judging the presence or absence of a specific component in the gas to be measured is combined with the concentration measuring method of the third invention for measuring the concentration of the specific component in the gas to be measured. , Gas detection and concentration measurement. That is, when at least one of the discharge breakdown voltage and the discharge sustaining voltage when the gas to be measured is discharged between the electrode pair, the gas to be measured contains the specific component as compared to the case where the gas to be measured does not contain the specific component. And the second characteristic in which the discharge current value when the gas to be measured is discharged between the electrode pair and the concentration of the specific component contained in the gas to be measured are correlated. Using the electrode pair having, the gas to be measured is discharged to measure at least one of a discharge breakdown voltage and a sustaining voltage, and a discharge current value, and the first component is used to measure the specific component in the gas to be measured. Judge the presence or absence of
The concentration of the specific component in the gas to be measured can be measured by the second characteristic.
【００２４】また、第２発明及び第４発明におけると同
様に、上記特定成分は２種以上であり、上記電極対は該
特定成分の各々に対応して上記第１特性及び第２特性を
有する２種以上であることにより、２種以上の特定成分
の有無の判定と、濃度の測定を行うことができる。Further, as in the second and fourth inventions, the specific component is two or more, and the electrode pair has the first characteristic and the second characteristic corresponding to each of the specific components. By using two or more types, it is possible to determine the presence or absence of two or more specific components and measure the concentration.
【００２５】第５発明のガスセンサは、被測定ガス中の
特定成分の有無により放電破壊電圧及び放電維持電圧の
少なくとも一方が変化する特性を有する電極対を備え、
該電極対間において該被測定ガスを放電させることを特
徴とする。A gas sensor according to a fifth aspect of the present invention includes an electrode pair having a characteristic that at least one of a discharge breakdown voltage and a discharge sustaining voltage changes depending on the presence or absence of a specific component in a gas to be measured.
The gas to be measured is discharged between the pair of electrodes.
【００２６】このガスセンサは、第１発明のガス検知方
法に用いることができるガスセンサであり、上記「被測
定ガス」、上記「特定成分」、上記「放電」、上記「特
性」及び上記「電極対」については第１発明におけると
同様である。更に、第６発明のように、２種以上の特定
成分の各々の電圧に対する感応性を有する、２種以上の
電極対を備えることで、第２発明のガス検知方法に用い
ることができる。但し、この第５発明及び第６発明のガ
スセンサは、必ずしも第１発明及び第２発明のガス検知
方法に用いる必要はなく、他のガス検知方法及びガス濃
度測定方法に用いてもよい。This gas sensor is a gas sensor that can be used in the gas detection method of the first invention, and includes the above-mentioned “gas to be measured”, the above “specific component”, the above “discharge”, the above “characteristics”, and the above “electrode pair”. Is the same as in the first invention. Furthermore, by providing two or more electrode pairs having sensitivity to each voltage of two or more specific components as in the sixth invention, it can be used in the gas detection method of the second invention. However, the gas sensors of the fifth and sixth aspects of the invention are not necessarily used for the gas detection methods of the first and second aspects, but may be used for other gas detection methods and gas concentration measurement methods.
【００２７】このようなガスセンサのより具体的な構成
として、第５発明のガスセンサでは、例えば、（１）被
測定ガスを導入するための被測定ガス導入口１３と被測
定ガスを外部に排出するための被測定ガス排出口１４と
を備える空間、及び、この空間内に備えられた一対の電
極１１ａ及び１１ｂを有するものが挙げられる（図１参
照）。更に、（２）被測定ガスを導入するための被測定
ガス導入口１３と被測定ガスを外部に排出するための被
測定ガス排出口１４とを備える空間、及び、この空間内
に一方の電極１１ａが設置され、他方の電極１１ｂが一
方の電極１１ａと微少な間隔を保ちながらこの空間の外
側に設置されたものが挙げられる（図２参照）。また、
第６発明のガスセンサでは、上記（１）の内部に電極対
を備える空間を２以上備えるものが挙げられる（図３参
照）。更に、（２）の空間内に設置される電極が複数の
電極対の一方の電極１１ｂの電極の役目を果たし、他方
の電極１１ｂは各々独立して空間外に設置されるものが
挙げられる（図４参照）。As a more specific configuration of such a gas sensor, the gas sensor according to the fifth aspect of the present invention includes, for example, (1) a measured gas inlet 13 for introducing a measured gas and discharging the measured gas to the outside. And a space having a pair of electrodes 11a and 11b provided in the space provided with the measured gas discharge port 14 (see FIG. 1). Further, (2) a space including a measured gas inlet 13 for introducing the measured gas and a measured gas outlet 14 for discharging the measured gas to the outside, and one electrode in the space. 11a, and the other electrode 11b is provided outside of this space while keeping a small distance from the one electrode 11a (see FIG. 2). Also,
The gas sensor according to the sixth aspect of the present invention includes a gas sensor having two or more spaces having electrode pairs inside the above (1) (see FIG. 3). Further, an electrode provided in the space of (2) serves as an electrode of one electrode 11b of a plurality of electrode pairs, and the other electrode 11b is independently provided outside the space. (See FIG. 4).
【００２８】第７発明のガスセンサは、電極対間にて被
測定ガスを放電させた場合の放電電流値と、該被測定ガ
ス中に含まれる特定成分の濃度とが相関する特性を有す
る該電極対を備え、該電極対間において該被測定ガスを
放電させることを特徴とする。According to a seventh aspect of the present invention, there is provided a gas sensor having a characteristic that a discharge current value when a gas to be measured is discharged between an electrode pair and a concentration of a specific component contained in the gas to be measured is correlated. A pair is provided, and the gas to be measured is discharged between the pair of electrodes.
【００２９】このガスセンサは、第３発明のガス濃度測
定方法に用いることができるガスセンサであり、上記
「被測定ガス」、上記「特定成分」、上記「放電」、上
記「特性」及び上記「電極対」については第３発明にお
けると同様である。更に、第８発明のように、２種以上
の特定成分の放電電流値の各々に感応性を有する、２種
以上の電極対を備えることで、第４発明のガス検知方法
に用いることができる。但し、この第７発明及び第８発
明のガスセンサは、必ずしも第３発明及び第４発明のガ
ス検知方法に用いる必要はなく、他のガス検知方法及び
ガス濃度測定方法に用いてもよい。This gas sensor is a gas sensor which can be used in the gas concentration measuring method of the third invention, and includes the above-mentioned "gas to be measured", "specific component", "discharge", "characteristic", and "electrode". The "pair" is the same as in the third invention. Further, by providing two or more electrode pairs having sensitivity to each of the two or more specific component discharge current values as in the eighth invention, it can be used in the gas detection method of the fourth invention. . However, the gas sensors of the seventh and eighth inventions are not necessarily used for the gas detection methods of the third and fourth inventions, but may be used for other gas detection methods and gas concentration measurement methods.
【００３０】第７発明のガスセンサのより具体的な構成
として、第５発明のガスセンサと度様な構成のものを挙
げることができる。更に、第８発明のガスセンサのより
具体的な構成として、第６発明と同様な構成のものを挙
げることができる。As a more specific configuration of the gas sensor of the seventh invention, a gas sensor having a configuration similar to that of the gas sensor of the fifth invention can be mentioned. Further, as a more specific configuration of the gas sensor of the eighth invention, a gas sensor having the same configuration as that of the sixth invention can be mentioned.
【００３１】また、第５発明に挙げるガスセンサの構成
を有し、このガスセンサの備える電極が第１発明に示す
放電破壊電圧又は放電維持電圧の少なくともいずれかに
対する感応性と、第３発明に示す放電電流値にする感応
性との両方を有することにより、特定成分の有無の判定
と、特定成分の濃度とを同時に測定することができるガ
スセンサを得ることができる。Further, the gas sensor according to the fifth aspect of the present invention has a configuration in which the electrodes of the gas sensor are sensitive to at least one of the discharge breakdown voltage and the discharge sustaining voltage according to the first aspect of the invention, and the discharge resistance according to the third aspect of the invention. By having both the sensitivity to the current value, it is possible to obtain a gas sensor that can simultaneously determine the presence or absence of a specific component and simultaneously measure the concentration of the specific component.
【００３２】[0032]
【発明の実施の形態】以下、本発明を実施例によって具
体的に説明する。 （１）ガス検知を目的とするガスセンサ及びこれを備え
るガス検知装置 図５に示すように、内径１０ｍｍ、外径１２ｍｍ、長さ
１５ｃｍ（この内、放電部分５ｃｍ）のガラス管１２内
に、銅（純度９９．９％）からなる直径８ｍｍ、長さ５
ｃｍの円柱状の電極１１ａ及び１１ｂをガラス管の両端
から支持し、電極対間の距離が２ｍｍとなるように配置
した。更に、このガラス管内にはガラス管の一端から被
測定ガスを流入させる被測定ガス導入口１３と、電極対
間を含む空間を通って他端から流出させることができる
被測定ガス排出口１４とを備えるガスセンサ１を形成し
た。DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described specifically with reference to examples. (1) Gas sensor for gas detection and gas detection device provided with the same As shown in FIG. 5, copper is placed in a glass tube 12 having an inner diameter of 10 mm, an outer diameter of 12 mm, and a length of 15 cm (of which 5 cm is a discharge portion). (Purity 99.9%) Diameter 8mm, Length 5
cm of columnar electrodes 11a and 11b were supported from both ends of the glass tube and arranged so that the distance between the electrode pairs was 2 mm. Furthermore, a measured gas inlet 13 through which a gas to be measured flows in from one end of the glass tube, and a measured gas outlet 14 through which the gas can flow out from the other end through a space including between the electrode pairs. Was formed.
【００３３】更に、上記の電極対に電圧を印加するため
のファンクションジェネレータ３を、ファンクションジ
ェネレータ３から出力された電圧を増幅する高電圧増幅
器２に接続し、この高電圧増幅器２を更に電極対に接続
した。また、被測定ガスを放電させるまでの電圧の波形
を観測するためのデジタルストレージオシロスコープ４
をガスセンサに接続してガス検知装置を形成した。Further, a function generator 3 for applying a voltage to the electrode pair is connected to a high voltage amplifier 2 for amplifying a voltage output from the function generator 3, and the high voltage amplifier 2 is further connected to the electrode pair. Connected. Also, a digital storage oscilloscope 4 for observing a voltage waveform until the gas to be measured is discharged.
Was connected to a gas sensor to form a gas detection device.
【００３４】（２）放電破壊電圧の測定 被測定ガスとして、Ｎ2８５％、ＣＯ2１０％、Ｏ2５％
のベースガスにＮＯを３００ｐｐｍ含有する第１モデル
ガス、同じベースガスにＮＯを６００ｐｐｍ含有する第
２モデルガス、同じベースガスにＮＯを９００ｐｐｍ含
有する第３モデルガスの３種を各々別々に上記ガス検知
装置内に１００ｍｌ／分で流入させ、３０分間この状態
を保った。その後、上記の電極対に周波数１ｋＨｚの正
弦波の電圧をファンクションジェネレータの出力を調節
して徐々に昇圧しながら印加し、グロー放電に移行する
直前の印加電圧（グロー放電破壊電圧）をデジタルスト
レージオシロスコープのリードアウト機能を使用して読
みとった。また、このグロー放電へ移行したことは、図
６に示すような波形が出力されることで確認した。その
結果、グロー放電破壊電圧とＮＯ濃度との間に緩やかな
正の相関関係が得られた。この結果を図７に示した。(2) Measurement of discharge breakdown voltage As a gas to be measured, N 2 85%, CO 2 10%, O 2 5%
The first model gas containing 300 ppm of NO in the base gas, the second model gas containing 600 ppm of NO in the same base gas, and the third model gas containing 900 ppm of NO in the same base gas. It was allowed to flow into the detection device at a rate of 100 ml / min, and this state was maintained for 30 minutes. Thereafter, a sine wave voltage having a frequency of 1 kHz is applied to the electrode pair while gradually increasing the output of the function generator by adjusting the output of the function generator. Was read using the readout function. The shift to the glow discharge was confirmed by outputting a waveform as shown in FIG. As a result, a gentle positive correlation was obtained between the glow discharge breakdown voltage and the NO concentration. The result is shown in FIG.
【００３５】[0035]
【発明の効果】第１発明のガス検知方法によると、広範
な測定条件において、組成が未知である混合ガス中に含
有されるあらゆる単一の成分ガスを検知することができ
る。また、第３発明によると、広範な測定条件におい
て、組成が未知である混合ガス中に含有されるあらゆる
単一の成分ガスの濃度を測定することができる。第５発
明によると、広範な測定条件において、組成が未知であ
る混合ガス中に含有されるあらゆる単一の成分ガスを検
知する場合に用いるガスセンサを得ることができる。第
７発明によると、広範な測定条件において、組成が未知
である混合ガス中に含有されるあらゆる単一の成分ガス
の濃度を測定する場合に用いるガスセンサを得ることが
できる。According to the gas detection method of the first invention, all single component gases contained in a mixed gas whose composition is unknown can be detected under a wide range of measurement conditions. Further, according to the third aspect, the concentration of every single component gas contained in the mixed gas whose composition is unknown can be measured under a wide range of measurement conditions. According to the fifth aspect, it is possible to obtain a gas sensor used for detecting all single component gases contained in a mixed gas whose composition is unknown under a wide range of measurement conditions. According to the seventh aspect, it is possible to obtain a gas sensor used for measuring the concentration of every single component gas contained in a mixed gas whose composition is unknown under a wide range of measurement conditions.
【図１】第５発明のガスセンサの一例を示す模式図であ
る。FIG. 1 is a schematic view showing an example of a gas sensor according to a fifth invention.
【図２】第５発明のガスセンサの他例を示す模式図であ
る。FIG. 2 is a schematic view showing another example of the gas sensor of the fifth invention.
【図３】第６発明のガスセンサの一例を示す模式図であ
る。FIG. 3 is a schematic view showing an example of a gas sensor according to a sixth invention.
【図４】第６発明のガスセンサの他例を示す模式図であ
る。FIG. 4 is a schematic view showing another example of the gas sensor of the sixth invention.
【図５】実施例で用いたガスセンサ及び測定装置の模式
図である。FIG. 5 is a schematic diagram of a gas sensor and a measurement device used in the example.
【図６】実施例において出力された放電維持電圧の波形
を説明する説明図である。FIG. 6 is an explanatory diagram illustrating a waveform of a sustaining voltage output in an example.
【図７】実施例において測定された放電破壊電圧と被測
定ガス濃度との相関を表すグラフである。FIG. 7 is a graph showing a correlation between a discharge breakdown voltage measured in an example and a gas concentration to be measured.
【符号の説明】 １；ガスセンサ、１１ａ及び１１ｂ；電極、１２；ガラ
ス管、１３；被測定ガス導入口、１４；被測定ガス排出
口、２；高圧増幅器、３；ファンクションジェネレー
タ、４；ディジタルストレージオシロスコープ。DESCRIPTION OF SYMBOLS 1; gas sensor, 11a and 11b; electrode, 12; glass tube, 13; measured gas inlet, 14; measured gas outlet, 2; high pressure amplifier, 3; function generator, 4; oscilloscope.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 林 佑二 神奈川県川崎市中原区上小田中1015番地 (72)発明者 山田 達也 愛知県名古屋市熱田区六野二丁目４番地１ 号 財団法人ファインセラミックスセンタ ー内 (72)発明者 島森 融 名古屋市瑞穂区高辻町14番18号 日本特殊 陶業株式会社内 (72)発明者 近藤 和夫 名古屋市瑞穂区高辻町14番18号 日本特殊 陶業株式会社内 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Yuji Hayashi 1015 Uedanaka, Nakahara-ku, Kawasaki-shi, Kanagawa Prefecture (72) Tatsuya Yamada 2-4-1 Rokuno, Atsuta-ku, Nagoya-shi, Aichi Japan Fine Ceramics Center -Inside (72) Inventor: Atsushi Shimamori, 14-18, Takatsuji-cho, Mizuho-ku, Nagoya-shi, Japan Inside (72) Inventor Kazuo Kondo, 14-18 Takatsuji-cho, Mizuho-ku, Nagoya, Japan
Claims (8)
合の放電破壊電圧及び放電維持電圧の少なくとも一方
が、該被測定ガス中の特定成分の有無により変化する特
性を有する該電極対を用いて、該被測定ガスを放電させ
て放電破壊電圧及び放電維持電圧の少なくとも一方を測
定し、該特性により該被測定ガス中の上記特定成分の有
無を判定することを特徴とするガス検知方法。An electrode pair having a characteristic that at least one of a discharge breakdown voltage and a discharge sustaining voltage when a gas to be measured is discharged between the pair of electrodes changes depending on the presence or absence of a specific component in the gas to be measured. Discharging the gas to be measured, measuring at least one of a discharge breakdown voltage and a discharge sustaining voltage, and determining the presence or absence of the specific component in the gas to be measured based on the characteristic. Method.
極対は該特定成分の各々に対応して上記特性を有する２
種以上である請求項１記載のガス検知方法。2. The method according to claim 1, wherein the specific component is at least two types, and the electrode pair has the above-described characteristic corresponding to each of the specific components.
The gas detection method according to claim 1, wherein the gas detection method is at least one kind.
合の放電電流値と、該被測定ガス中に含まれる特定成分
の濃度とが相関する特性を有する該電極対を用いて、該
被測定ガスを放電させて放電電流値を測定し、該特性に
より該被測定ガス中の上記特定成分の濃度を測定するこ
とを特徴とするガス濃度測定方法。3. Using the electrode pair having a characteristic in which a discharge current value when a gas to be measured is discharged between the electrode pair and a concentration of a specific component contained in the gas to be measured is correlated. A gas concentration measuring method comprising: discharging a gas to be measured; measuring a discharge current value; and measuring a concentration of the specific component in the gas to be measured based on the characteristic.
極対は該特定成分の各々に対応して上記特性を有する２
種以上である請求項３記載のガス検知方法。4. The method according to claim 1, wherein the specific component is at least two types, and the electrode pair has the above-described characteristic corresponding to each of the specific components.
4. The gas detection method according to claim 3, wherein the gas detection method is at least one kind.
電破壊電圧及び放電維持電圧の少なくとも一方が変化す
る特性を有する電極対を備え、該電極対間において該被
測定ガスを放電させることを特徴とするガスセンサ。5. An electrode pair having a characteristic that at least one of a discharge breakdown voltage and a discharge sustaining voltage changes depending on the presence or absence of a specific component in a gas to be measured, and discharging the gas to be measured between the pair of electrodes. Characteristic gas sensor.
に対応して上記特性を各々有する２種以上である請求項
５記載のガスセンサ。6. The gas sensor according to claim 5, wherein the electrode pairs are two or more kinds each having the above-described characteristics corresponding to two or more kinds of the specific components.
合の放電電流値と、該被測定ガス中に含まれる特定成分
の濃度とが相関する特性を有する該電極対を備え、該電
極対間において該被測定ガスを放電させることを特徴と
するガスセンサ。7. An electrode pair having a characteristic in which a discharge current value when a gas to be measured is discharged between the electrode pair and a concentration of a specific component contained in the gas to be measured is provided. A gas sensor wherein the gas to be measured is discharged between electrode pairs.
に対応して上記特性を各々有する２種以上である請求項
７記載のガスセンサ。8. The gas sensor according to claim 7, wherein the electrode pairs are two or more kinds each having the above-described characteristics corresponding to two or more kinds of the specific components.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000366136A JP2002168832A (en) | 2000-11-30 | 2000-11-30 | Gas detecting method and gas-concentration measuring method as well as gas sensor |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000366136A JP2002168832A (en) | 2000-11-30 | 2000-11-30 | Gas detecting method and gas-concentration measuring method as well as gas sensor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2002168832A true JP2002168832A (en) | 2002-06-14 |
Family
ID=18836804
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000366136A Pending JP2002168832A (en) | 2000-11-30 | 2000-11-30 | Gas detecting method and gas-concentration measuring method as well as gas sensor |
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| Country | Link |
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| CN100403022C (en) * | 2004-06-17 | 2008-07-16 | 西安交通大学 | Self-hold dark discharge carbon nanometer pipe film gas sensor and its gas concentration measuring method |
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| JPWO2015115245A1 (en) * | 2014-01-29 | 2017-03-23 | 株式会社リコー | COMMUNICATION DEVICE, COMMUNICATION SYSTEM, COMMUNICATION METHOD, AND STORAGE MEDIUM |
| CN110095529A (en) * | 2019-05-08 | 2019-08-06 | 中国电力科学研究院有限公司 | A kind of environmental protection effect appraisal procedure of perfluor isobutyronitrile mixed gas |
| CN111739783A (en) * | 2020-05-28 | 2020-10-02 | 清华大学 | Atmospheric pressure electric arc ion source for small mass spectrometer and detection method thereof |
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| CN111739783B (en) * | 2020-05-28 | 2021-10-29 | 清华大学 | Atmospheric pressure electric arc ion source for small mass spectrometer and detection method thereof |
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