JP2010190752A - Gas sensor and gas detector - Google Patents
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Abstract
Description
本発明は、所定組成のガスを検出するためのガスセンサ、及び該ガスセンサを備えるガス検出装置に関する。 The present invention relates to a gas sensor for detecting a gas having a predetermined composition, and a gas detection apparatus including the gas sensor.
生体の呼気には複数の組成のガスが含まれているが、かかる呼気中に含まれるアンモニアガスを検出するガスセンサとして後記するが特許文献１には次のようなものが開示されている。 The exhaled breath of a living body contains a plurality of gas compositions. As described later as a gas sensor for detecting ammonia gas contained in the exhaled breath, Patent Document 1 discloses the following.
すなわち、セラミックス基板上に一対の櫛歯状の電極を互いに適宜距離隔てて形成し、両電極間に、ポリアニリンスルホン酸樹脂とバインダとしてスルホン酸塩とを質量比で９：１になるように混合させた混合物を充填することによってガスセンサを得る。 That is, a pair of comb-like electrodes are formed on a ceramic substrate at an appropriate distance from each other, and a polyaniline sulfonic acid resin and a sulfonate as a binder are mixed at a mass ratio of 9: 1 between both electrodes. A gas sensor is obtained by filling the mixed mixture.
かかるガスセンサにあっては、ポリアニリンスルホン酸樹脂がアンモニアガスと相互反応して両電極間の電気抵抗が変化するので、当該電気抵抗の変化量を測定することによってアンモニアガスの濃度を検出することができる。 In such a gas sensor, since the polyaniline sulfonic acid resin interacts with ammonia gas and the electrical resistance between both electrodes changes, it is possible to detect the concentration of ammonia gas by measuring the amount of change in the electrical resistance. it can.
しかし、特許文献１に開示されたガスセンサにあっては、両電極間に充填したポリアニリンスルホン酸樹脂層が密であるため、ガス検出の感度が低いという問題があった。 However, the gas sensor disclosed in Patent Document 1 has a problem that the sensitivity of gas detection is low because the polyaniline sulfonic acid resin layer filled between both electrodes is dense.
そのため、例えばアニリン溶液と重合剤たるＡＳＰ（Ammonium peroxydisulfate）溶液とを高速に撹拌しつつ混合させて、アニリンポリマーを重合させると共に、複数のアニリンポリマーが集合したファイバを生成させ、複数のファイバが重積された層を両電極間に堆積させてなるガスセンサが開発されている。 Therefore, for example, an aniline solution and an ASP (Ammonium peroxydisulfate) solution, which is a polymerization agent, are mixed while stirring at a high speed to polymerize the aniline polymer and to produce a fiber in which a plurality of aniline polymers are aggregated. A gas sensor has been developed in which a stacked layer is deposited between both electrodes.
かかるガスセンサでは、各ファイバ間に間隙が形成されているため、アンモニアガスが内部へ侵入する量が増大し、検出感度が向上する。 In such a gas sensor, since a gap is formed between the fibers, the amount of ammonia gas entering the interior increases, and the detection sensitivity is improved.
しかしながら、このような従来のいずれのガスセンサにあっても、対をなす電極間に充填したポリアニリン層をより薄くすることによって検出感度を向上させることができるが、所定厚さ以下すると、電気抵抗の変化を検出することができないため、検出感度を向上させるには限度があった。このようにいずれのガスセンサにあっても、ポリアニリン層は適宜の厚さが必要であるため、ガス検出の応答速度が遅いという問題もあった。更に、いずれのガスセンサにあっても、ポリアニリン層の内部に侵入したアンモニアガスが層外に排出され難く、当該ガスセンサを繰り返し使用することが困難であった。 However, in any of such conventional gas sensors, the detection sensitivity can be improved by making the polyaniline layer filled between the pair of electrodes thinner. Since changes cannot be detected, there was a limit to improving detection sensitivity. As described above, in any gas sensor, since the polyaniline layer needs to have an appropriate thickness, there is a problem that the response speed of gas detection is slow. Further, in any gas sensor, ammonia gas that has entered the inside of the polyaniline layer is difficult to be discharged out of the layer, and it is difficult to repeatedly use the gas sensor.
本発明は、斯かる事情に鑑みてなされたものであって、より高い検出感度でより迅速に検出ことができ、また繰り返し使用も可能なガスセンサ、及び該ガスセンサを備えるガス検出装置を提供する。 The present invention has been made in view of such circumstances, and provides a gas sensor that can be detected more quickly with higher detection sensitivity and can be repeatedly used, and a gas detection device including the gas sensor.
（１）本発明に係るガスセンサは、基板の表面に適宜距離を隔てて配置した対をなす電極間を、検出対象ガスと相互反応して電気伝導度が変化する有機ポリマで架橋してなるガスセンサにおいて、前記基板の両電極間の領域に導電性を有する所要の金属粒子複数が互に適宜のギャップを隔てて形成してあり、前記有機ポリマにて構成された複数のファイバによって任意の複数の金属粒子間及び前記両電極と任意の金属粒子との間をそれぞれ架橋することによって、両電極間を架橋する前記各ファイバのネットワークが形成してあることを特徴とする。 (1) A gas sensor according to the present invention is a gas sensor formed by bridging a pair of electrodes arranged on a surface of a substrate at an appropriate distance with an organic polymer whose electrical conductivity changes by interacting with a detection target gas. In the present invention, a plurality of required metal particles having conductivity are formed in a region between both electrodes of the substrate with an appropriate gap from each other, and a plurality of arbitrary fibers can be formed by a plurality of fibers made of the organic polymer. A network of the fibers that bridge between the electrodes is formed by crosslinking between the metal particles and between the electrodes and any metal particles.
（２）本発明に係るガスセンサは必要に応じて、主にアンモニアガスを検出対象ガスとすべく、前記有機ポリマをポリアニリンで構成してあり、前記両電極の所要領域の表面及び各金属粒子の表面にそれぞれ４−アミノチオフェンを化学結合させてあり、これら４−アミノチオフェンに任意のファイバが化学結合していることを特徴とする。 (2) In the gas sensor according to the present invention, the organic polymer is composed of polyaniline so that ammonia gas is mainly used as a detection target gas as necessary. 4-aminothiophene is chemically bonded to each surface, and an arbitrary fiber is chemically bonded to these 4-aminothiophenes.
（３）本発明に係るガスセンサは必要に応じて、前記ネットワークは、対をなす電極間に有機ポリマの原料溶液と重合剤溶液とを混合した混合液を供給し、略０℃以上略２０℃以下の適宜の温度でファイバを生成させることによって形成してあることを特徴とする。 (3) In the gas sensor according to the present invention, the network supplies a mixed liquid obtained by mixing the organic polymer raw material solution and the polymerizing agent solution between the paired electrodes as necessary, and is approximately 0 ° C. or higher and approximately 20 ° C. It is formed by generating a fiber at the following appropriate temperature.
（４）本発明に係るガスセンサは必要に応じて、前記ギャップは対をなす電極間の電気抵抗が数ギガΩになるように調整してあることを特徴とする。 (4) The gas sensor according to the present invention is characterized in that the gap is adjusted so that the electrical resistance between the paired electrodes is several gigaΩ as required.
（５）本発明に係るガス検出装置は、基板の表面に適宜距離を隔てて配置した対をなす電極間を、検出対象ガスと相互反応して電気伝導度が変化する有機ポリマで架橋してなるガスセンサを備え、前記両電極間の電気伝導度の変化によって検出対象ガスを検出するガス検出装置において、前述したいずれかに記載のガスセンサを備えることを特徴とする。 (5) In the gas detection device according to the present invention, a pair of electrodes arranged at an appropriate distance on the surface of the substrate is cross-linked with an organic polymer that interacts with the detection target gas and changes electrical conductivity. A gas detection apparatus that detects a detection target gas by a change in electrical conductivity between the electrodes, and includes any of the gas sensors described above.
（本発明の実施形態）
図１は本発明に係るガス検出装置の構成を模式的要部拡大図と共に示すブロック図であり、図中、２は検出対象ガスが導入される中空のチャンバである。
チャンバ２内にはガス導入管及びガス排出管の一端部がそれぞれ挿入してあり、ガス導入管及びガス排出管の他端部はチャンバ２の外方へ延出してある。かかるガス導入管の他端は、ポンプ及び流量調整器等を内蔵するガス導入器１のガス送出口に連結してあり、ガス導入器１から送出されたガスはガス導入管を経てチャンバ２内へ導入され、該チャンバ２内に一時的に貯留された後、ガス排出管によってチャンバ２外へ排出される。
(Embodiment of the present invention)
FIG. 1 is a block diagram showing a configuration of a gas detection device according to the present invention together with a schematic enlarged view of a main part. In the figure, 2 is a hollow chamber into which a detection target gas is introduced.
One end portions of a gas introduction tube and a gas discharge tube are respectively inserted into the chamber 2, and the other end portions of the gas introduction tube and the gas discharge tube extend to the outside of the chamber 2. The other end of the gas introduction pipe is connected to a gas delivery port of the gas introduction apparatus 1 incorporating a pump and a flow rate regulator, and the gas delivered from the gas introduction apparatus 1 passes through the gas introduction pipe and enters the chamber 2. After being temporarily stored in the chamber 2, it is discharged out of the chamber 2 by a gas discharge pipe.
このチャンバ２内には所定組成のガスを検出するガスセンサ３が配設してある。ガスセンサ３は硝子といった適宜の基板３１の表面に適宜のギャップを隔てて一対の電極３２，３２が設けてあり、両電極３２，３２にはそれぞれリード３２ａ，３２ａが連結してある。 A gas sensor 3 for detecting a gas having a predetermined composition is disposed in the chamber 2. In the gas sensor 3, a pair of electrodes 32 and 32 are provided on the surface of an appropriate substrate 31 such as glass with an appropriate gap therebetween, and leads 32a and 32a are connected to the electrodes 32 and 32, respectively.
この電極３２，３２間に、如く有機ポリマを用いて形成してあるナノサイズの直径のファイバにて後述する形成したネットワーク３６（図２参照）が架設してあり、両電極３２，３２間の電気抵抗は検出器４によって検出されるようになっている。検出器４には両電極３２，３２間の電気抵抗とガス濃度との関係を示す係数が予め設定してあり、検出器４は当該係数及び検出した両電極３２，３２間の電気抵抗に基づいて検出対象ガスの濃度を検出する。
なお、電極３２，３２は平板状、櫛歯状等、種々の形状になすことができる。
Between the electrodes 32 and 32, a network 36 (see FIG. 2), which will be described later, is constructed by a nano-sized fiber formed using an organic polymer as described above. The electrical resistance is detected by the detector 4. A coefficient indicating the relationship between the electric resistance between the electrodes 32 and 32 and the gas concentration is preset in the detector 4, and the detector 4 is based on the coefficient and the detected electric resistance between the electrodes 32 and 32. To detect the concentration of the detection target gas.
In addition, the electrodes 32 and 32 can be made into various shapes such as a flat plate shape and a comb shape.
図２は、図１に示したガスセンサ３の製造手順を説明する説明図である。
図２（ａ）に示した如く、基板３１の表面に、対をなす電極３２，３２及びリード３２ａ，３２ａ（図１参照）を適宜のギャップを隔ててパターニングする。かかるパターニングは、例えばフォトリソグラフィ法及び蒸着法を用いて行うことができる。また、電極３２，３２及びリード３２ａ，３２ａの材料としては、検出対象ガス及び有機ポリマの種類等に応じて金、銀、白金等、導電性を有する適当な金属を用いる。
FIG. 2 is an explanatory view for explaining a manufacturing procedure of the gas sensor 3 shown in FIG.
As shown in FIG. 2A, a pair of electrodes 32 and 32 and leads 32a and 32a (see FIG. 1) are patterned on the surface of the substrate 31 with an appropriate gap therebetween. Such patterning can be performed using, for example, a photolithography method and a vapor deposition method. In addition, as the materials of the electrodes 32 and 32 and the leads 32a and 32a, an appropriate conductive metal such as gold, silver, or platinum is used according to the detection target gas and the type of the organic polymer.
一方、電極３２，３２のギャップは５μｍ程度〜２００μｍ程度に設定する。
次に、図２（ｂ）に示した如く、電極３２，３２と同じ材料を用いて、直径がナノサイズの複数の金属粒子３３，３３，…を、両電極３２，３２間の電気抵抗が数〜数百ギガΩ程度になるように互いに適宜のギャップを隔てて生成させる。
On the other hand, the gap between the electrodes 32 and 32 is set to about 5 μm to 200 μm.
Next, as shown in FIG. 2 (b), using the same material as the electrodes 32, 32, a plurality of metal particles 33, 33,. They are generated with an appropriate gap from each other so as to be about several to several hundred gigaΩ.
金属粒子３３，３３，…の生成はスパッタリングによって行うことができる。また、各金属粒子３３，３３，…間のギャップは、スパッタリング装置における作動電流値及びスパッタリングを行う時間によって調整することができ、両電極３２，３２間の電気抵抗がギガΩ程度になるように各金属粒子３３，３３，…間のギャップを調整する。
例えば、アルバック社のＵＰＳ０５０型のスパッタリング装置を用いた場合、アルゴンガス中、５ｍＡで９０秒程度のスパッタリングを行うことが好適である。
Generation of the metal particles 33, 33,... Can be performed by sputtering. Further, the gap between the metal particles 33, 33,... Can be adjusted by the operating current value in the sputtering apparatus and the sputtering time, so that the electrical resistance between the electrodes 32, 32 is about giga Ω. The gap between each metal particle 33,33, ... is adjusted.
For example, when using a UPS 050 type sputtering apparatus manufactured by ULVAC, it is preferable to perform sputtering in argon gas at 5 mA for about 90 seconds.
図３は、互いにギャップを隔てて形成した金属粒子３３，３３，…の原子間力顕微鏡写真図である。図３から明らかなように、金属粒子３３，３３，…は略球状をなしており、従って各金属粒子３３，３３，…の間にはギャップが存在することが分かる。 FIG. 3 is an atomic force micrograph of metal particles 33, 33,... Formed with a gap therebetween. As is apparent from FIG. 3, the metal particles 33, 33,... Have a substantially spherical shape, and thus it can be seen that a gap exists between the metal particles 33, 33,.
次に、ガスセンサ３の表面の両電極３２，３２及びその間隙領域を除く領域を被覆した後、必要に応じて図２（ｃ）に示した如く、金属粒子３３，３３，…及び電極３２，３２に結合する部位と前述したファイバに結合する部位とを備える官能基３４，３４，…を金属粒子３３，３３，…及び電極３２，３２の表面に化学的に結合させる。 Next, after covering both the electrodes 32, 32 on the surface of the gas sensor 3 and the region excluding the gap region, as shown in FIG. 2 (c), the metal particles 33, 33,. Are bonded to the surfaces of the metal particles 33, 33,... And the electrodes 32, 32. The functional groups 34, 34,.
金属粒子３３，３３，…及び電極３２，３２への官能基３４，３４，…の接合は、適宜の溶媒に官能基３４，３４，…を溶解させた溶液に基板３１を浸漬させ、該溶液から引き出した基板３１を乾燥させることによって実施することができる。 The bonding of the functional groups 34, 34,... To the metal particles 33, 33,... And the electrodes 32, 32 is performed by immersing the substrate 31 in a solution in which the functional groups 34, 34,. It can be carried out by drying the substrate 31 drawn from the substrate.
ここで、検出対象ガスがアンモニアガスである場合、官能基３４，３４，…には４−アミノチオフェン（ＡＴＰ）を用いることができる。かかるＡＴＰは、金属結合部位としてチオール基を、またファイバ結合部位としてアミノ基を有している。 Here, when the detection target gas is ammonia gas, 4-aminothiophene (ATP) can be used for the functional groups 34, 34,. Such ATP has a thiol group as a metal binding site and an amino group as a fiber binding site.
また、ＡＴＰ以外にもファイバを構成するポリマの種類に応じて、カルボキシル基、水酸基、アンモニウム基、ピリジン、又はチオフェンをファイバ結合部位又は金属結合部位として有する官能基を用いることができる。 In addition to ATP, a functional group having a carboxyl group, a hydroxyl group, an ammonium group, pyridine, or thiophene as a fiber binding site or a metal binding site can be used depending on the type of polymer constituting the fiber.
次に、図２（ｄ）に示した如く、前述した任意の金属粒子３３，３３，…間、及び両電極３２，３２と任意の金属粒子３３，３３，…との間を複数のファイバ３５，３５，…で架橋することによってネットワーク３６を形成し、該ネットワーク３６によって両電極３２，３２間を架橋する。 Next, as shown in FIG. 2 (d), a plurality of fibers 35 are formed between the arbitrary metal particles 33, 33,... And between the electrodes 32, 32 and the arbitrary metal particles 33, 33,. , 35,... To form a network 36, and the network 36 bridges the electrodes 32, 32.
ネットワーク３６の形成は次のようにして行う。すなわち、有機ポリマの原料を適宜の溶媒に溶解させた原料溶液と、所要の重合剤を溶解させた重合剤溶液とを０℃程度から２０℃程度のまでの適宜の温度になし、両溶液を撹拌させながら混合させて混合液を得、この混合液を基板３１の両電極３２，３２間に供給した後、基板３１を０℃程度から２０℃程度のまでの適宜の温度下で静置して、原料の重合による有機ポリマの生成及び複数の有機ポリマの集合によるファイバ３５，３５，…の形成を実行させる。形成された各ファイバ３５，３５，…は、官能基３４，３４，…が結合されていない場合は金属粒子３３，３３，…に直接化学的に結合し、一方、官能基３４，３４，…が結合されている場合は当該官能基３４，３４，…を介して金属粒子３３，３３，…と化学的に結合して、ネットワーク３６が形成される。 The network 36 is formed as follows. That is, a raw material solution in which an organic polymer raw material is dissolved in an appropriate solvent and a polymer agent solution in which a required polymerization agent is dissolved are set to appropriate temperatures from about 0 ° C. to about 20 ° C., and both solutions are used. The mixture is mixed with stirring to obtain a mixed solution. After the mixed solution is supplied between the electrodes 32 and 32 of the substrate 31, the substrate 31 is allowed to stand at an appropriate temperature from about 0 ° C to about 20 ° C. Then, the production of the organic polymer by polymerization of the raw materials and the formation of the fibers 35, 35,... By the assembly of the plurality of organic polymers are executed. The formed fibers 35, 35,... Are directly chemically bonded to the metal particles 33, 33,... When the functional groups 34, 34,. Are chemically bonded to the metal particles 33, 33,... Via the functional groups 34, 34,.
ここで、有機ポリマとしては、検出対象ガスがアンモニアガスである場合はポリアニリンが好適である。例えば、３．２ｍｍｏｌ／ｌ（１Ｍ ＨＣｌ）のアニリン溶液１０ｍｌと、０．８ｍｍｏｌ／ｌ（１Ｍ ＨＣｌ）のＡＰＳ溶液１０ｍｌとを撹拌・混合させてポリアニリンのファイバを形成させる。なお、かかる操作中、溶液の温度を０℃から４℃に保持すると、ファイバの直径を３００ｎｍから５００ｎｍに制御できるため好適である。 Here, as the organic polymer, polyaniline is suitable when the detection target gas is ammonia gas. For example, 10 ml of an aniline solution of 3.2 mmol / l (1M HCl) and 10 ml of an APS solution of 0.8 mmol / l (1M HCl) are stirred and mixed to form a polyaniline fiber. Note that it is preferable to keep the temperature of the solution from 0 ° C. to 4 ° C. during the operation because the fiber diameter can be controlled from 300 nm to 500 nm.
一方、検出対象ガスの種類に応じて、チオフェン、ペプチド、アレーン、ピリジン、アセチレン、アルキル、アルケン系の基材からなる有機ポリマを用いることができる。
そして、混合液を基板３１の両電極３２，３２間に供給してから適宜時間経過した後、基板３１の表面を洗浄し、金属粒子３３，３３，…又は電極３２，３２に結合していないファイバを除去、基板３１の表面を乾燥させることによってガスセンサ３を得る。
On the other hand, an organic polymer composed of a thiophene, peptide, arene, pyridine, acetylene, alkyl, or alkene base material can be used depending on the type of detection target gas.
Then, after an appropriate time has elapsed since the mixed solution was supplied between the electrodes 32 and 32 of the substrate 31, the surface of the substrate 31 was washed and not bonded to the metal particles 33, 33,. The gas sensor 3 is obtained by removing the fiber and drying the surface of the substrate 31.
図４は、ガスセンサ３を構成するネットワーク３６のレーザ顕微鏡写真図である。
図４から明らかな如く、ネットワークは適宜の間隙を有しており、ネットワークを構成する各ファイバは略一次元状に展開されていると言える。
FIG. 4 is a laser micrograph of the network 36 constituting the gas sensor 3.
As is clear from FIG. 4, the network has an appropriate gap, and it can be said that the fibers constituting the network are developed in a substantially one-dimensional manner.
このようなガスセンサ３を備えるガス検出装置にあっては、ネットワーク３６を構成するファイバ３５，３５，…が両電極３２，３２及び金属粒子３３，３３，…と、官能基３４，３４，…を介して又は直接的、化学的に結合しているため、結合部の電気抵抗が低く、それに伴ってガスの検出感度が向上する。また、前述した如くネットワーク３６を構成する各ファイバ３５，３５，…は略一次元状に展開されているため、ネットワーク３６の厚さ寸法は可及的に薄く、これによってもガスの検出感度が向上する。 In the gas detection device including such a gas sensor 3, the fibers 35, 35,... Constituting the network 36 include both electrodes 32, 32 and metal particles 33, 33,. Therefore, the bonding portion has a low electrical resistance, and the gas detection sensitivity is improved accordingly. Further, as described above, since the fibers 35, 35,... Constituting the network 36 are developed in a substantially one-dimensional shape, the thickness dimension of the network 36 is as thin as possible, which also increases the gas detection sensitivity. improves.
一方、ネットワーク３６は適宜の間隙を有しているため、該ネットワーク３６が検出対象ガスの出入りに障壁とならず、検出対象ガスがネットワーク３６から外へ容易に排出される。したがって、ガスセンサ３を繰り返し使用することができる。 On the other hand, since the network 36 has an appropriate gap, the network 36 does not become a barrier to the entry and exit of the detection target gas, and the detection target gas is easily discharged out of the network 36. Therefore, the gas sensor 3 can be used repeatedly.
（実施例１）
次に、アンモニアガスを検出すべく、ポリアニリンのファイバによってネットワークを形成してなるガスセンサのガス検出感度を比較した結果について説明する。
Example 1
Next, the results of comparing the gas detection sensitivities of gas sensors formed by forming a network with polyaniline fibers to detect ammonia gas will be described.
図５は、ＡＴＰを結合させた金属粒子にポリアニリンのファイバによってネットワークを形成してなるガスセンサ（上位のグラフ）のガス検出感度と、ＡＴＰを結合させていない金属粒子にポリアニリンのファイバによってネットワークを形成してなるガスセンサ（下位のグラフ）のガス検出感度を比較した結果を示すグラフである。 Fig. 5 shows the gas detection sensitivity of a gas sensor (upper graph) formed by forming a network with polyaniline fibers on metal particles bonded with ATP, and the network formed with polyaniline fibers on metal particles not bonded with ATP. It is a graph which shows the result of having compared the gas detection sensitivity of the gas sensor (lower graph) formed.
図５から明らかな如く、前者のガス検出感度は後者のガス検出感度より略２倍〜略３倍高い結果であった。
この結果より、ネットワークを構成するファイバが両電極及び金属粒子と、官能基を介して化学的に結合しているため、結合部の電気抵抗が低く、それに伴ってガスの検出感度が向上することが分かる。
As is clear from FIG. 5, the former gas detection sensitivity was about 2 to 3 times higher than the latter gas detection sensitivity.
From this result, since the fibers constituting the network are chemically bonded to both electrodes and metal particles via functional groups, the electrical resistance of the bonded portion is low, and the gas detection sensitivity is improved accordingly. I understand.
（実施例２）
図６は実施例１で説明した本発明に係るガスセンサによって５ｐｐｍのアンモニアガスを経時的に検出した結果を示すグラフであり、図８及び図９は、従来のガスセンサによって１００ｐｐｍのアンモニアガスを経時的に検出した結果を示すグラフである。なお、図８で用いたガスセンサは対をなす電極間をポリアニリン膜で架橋してあり、図９で用いたガスセンサは対をなす電極をポリアニリンにて生成したファイバを重積させることによって架橋してある。また、両図８及び図９中、高段のグラフから下段のグラフにかけてポリアニリンの厚さを０．２μｍ〜２．０μｍ内で段階的に厚くしてある。
(Example 2)
FIG. 6 is a graph showing the results of detecting 5 ppm of ammonia gas over time by the gas sensor according to the present invention described in Example 1, and FIGS. 8 and 9 are graphs showing 100 ppm of ammonia gas over time by the conventional gas sensor. It is a graph which shows the result detected. The gas sensor used in FIG. 8 has a pair of electrodes cross-linked with a polyaniline film, and the gas sensor used in FIG. 9 cross-links the pair of electrodes by stacking fibers made of polyaniline. is there. In both FIGS. 8 and 9, the thickness of the polyaniline is increased stepwise from 0.2 μm to 2.0 μm from the upper graph to the lower graph.
これら図６と図８及び図９との比較から明らかなように、従来のガスセンサにあっては１００ｐｐｍと比較的高濃度のアンモニアガスであっても電気抵抗のシャープな変化を得ることが難しく、その変化にも数百秒と長時間を要していた。 As is clear from the comparison between FIG. 6 and FIGS. 8 and 9, it is difficult to obtain a sharp change in electrical resistance even with a relatively high concentration of ammonia gas of 100 ppm in the conventional gas sensor, The change required several hundred seconds and a long time.
これに対して、本発明に係るガスセンサにあっては、５ｐｐｍと１／２０の低濃度のアンモニアガスであっても、電気抵抗のシャープな変化を得ることができ、またその変化も略２０秒程度と短時間であった。 On the other hand, in the gas sensor according to the present invention, a sharp change in electrical resistance can be obtained even with ammonia gas having a low concentration of 5 ppm and 1/20, and the change is approximately 20 seconds. It was about a short time.
（実施例３）
図７は実施例１で説明した本発明に係るガスセンサによってアンモニアガスを繰り返し検出した結果を示すグラフである。
ガスセンサにアンモニアガスを１Ｌ／分の流量で３分間導入した後、ガスセンサに空気を２Ｌ／分の流量で５分間導入して洗浄する操作を繰り返し、ガスセンサの両電極間の電気抵抗を経時的に測定した。
(Example 3)
FIG. 7 is a graph showing the results of repeatedly detecting ammonia gas by the gas sensor according to the present invention described in Example 1.
After introducing ammonia gas into the gas sensor at a flow rate of 1 L / min for 3 minutes, air was introduced into the gas sensor at a flow rate of 2 L / min for 5 minutes and washing was repeated, and the electrical resistance between both electrodes of the gas sensor was changed over time. It was measured.
図７から明らかなように、本発明に係るガスセンサにあっては繰り返し使用した場合であってもガスセンサの両電極間の電気抵抗には僅かな上昇しか認められなかった。かかる電気抵抗の上昇は容易に校正することができるので、本発明に係るガスセンサは繰り返し使用することができる。 As is clear from FIG. 7, in the gas sensor according to the present invention, only a slight increase was observed in the electrical resistance between both electrodes of the gas sensor even when it was repeatedly used. Since such an increase in electrical resistance can be easily calibrated, the gas sensor according to the present invention can be used repeatedly.
１ ガス導入器
２ チャンバ
３ ガスセンサ
４ 検出器
３１ 基板
３２ 電極
３２ａ リード
３３ 金属粒子
３４ 官能基
３５ ファイバ
３６ ネットワーク
DESCRIPTION OF SYMBOLS 1 Gas introducing device 2 Chamber 3 Gas sensor 4 Detector 31 Substrate 32 Electrode 32a Lead 33 Metal particle 34 Functional group 35 Fiber 36 Network
Claims (5)
前記基板の両電極間の領域に導電性を有する所要の金属粒子複数が互に適宜のギャップを隔てて形成してあり、前記有機ポリマにて構成された複数のファイバによって任意の複数の金属粒子間及び前記両電極と任意の金属粒子との間をそれぞれ架橋することによって、両電極間を架橋する前記各ファイバのネットワークが形成してあることを特徴とするガスセンサ。 In a gas sensor formed by bridging a pair of electrodes arranged on the surface of the substrate at an appropriate distance with an organic polymer that interacts with a detection target gas and changes electrical conductivity,
A plurality of required metal particles having conductivity are formed in a region between both electrodes of the substrate with an appropriate gap therebetween, and a plurality of arbitrary metal particles are formed by a plurality of fibers composed of the organic polymer. The gas sensor is characterized in that a network of the fibers for bridging the electrodes is formed by bridging the electrodes and the electrodes and any metal particles.
請求項１から４のいずれかに記載のガスセンサを備えることを特徴とするガス検出装置。 A gas sensor is formed by bridging a pair of electrodes arranged on the surface of the substrate at an appropriate distance with an organic polymer whose electrical conductivity changes by interacting with the detection target gas, and the electric conduction between the electrodes. In the gas detection device that detects the detection target gas by the change in the degree,
A gas detection apparatus comprising the gas sensor according to claim 1.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111307883A (en) * | 2020-03-19 | 2020-06-19 | 中国石油大学(华东) | Preparation method of ammonia gas sensor based on polyaniline-vanadium carbide, detection system and application thereof |
| CN116334948A (en) * | 2023-03-03 | 2023-06-27 | 金陵科技学院 | Polypyrrole/silver/cellulose composite paper-based material, and preparation method and application thereof |
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| JP2003139775A (en) * | 2001-07-19 | 2003-05-14 | Sony Internatl Europ Gmbh | Chemical sensor, method of manufacturing chemical sensor, and method of detecting specimen |
| JP2003161714A (en) * | 2001-11-27 | 2003-06-06 | Ngk Spark Plug Co Ltd | Ammonia gas sensor and its manufacturing method |
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| JPH02304340A (en) * | 1989-05-18 | 1990-12-18 | Ryutoku Yosomiya | Ammonia sensor |
| JP2002228616A (en) * | 2000-12-12 | 2002-08-14 | Sony Internatl Europ Gmbh | Chemical sensor, method of manufacturing the same, and specimen detection method |
| JP2003139775A (en) * | 2001-07-19 | 2003-05-14 | Sony Internatl Europ Gmbh | Chemical sensor, method of manufacturing chemical sensor, and method of detecting specimen |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111307883A (en) * | 2020-03-19 | 2020-06-19 | 中国石油大学(华东) | Preparation method of ammonia gas sensor based on polyaniline-vanadium carbide, detection system and application thereof |
| CN111307883B (en) * | 2020-03-19 | 2021-12-28 | 中国石油大学(华东) | Preparation method of ammonia gas sensor based on polyaniline-vanadium carbide, detection system and application thereof |
| CN116334948A (en) * | 2023-03-03 | 2023-06-27 | 金陵科技学院 | Polypyrrole/silver/cellulose composite paper-based material, and preparation method and application thereof |
| CN116334948B (en) * | 2023-03-03 | 2024-04-19 | 金陵科技学院 | Polypyrrole/silver/cellulose composite paper-based material, and preparation method and application thereof |
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