JP2005221428A - Reducing gas detecting element, and reducing gas detector - Google Patents
Reducing gas detecting element, and reducing gas detector Download PDFInfo
- Publication number
- JP2005221428A JP2005221428A JP2004030924A JP2004030924A JP2005221428A JP 2005221428 A JP2005221428 A JP 2005221428A JP 2004030924 A JP2004030924 A JP 2004030924A JP 2004030924 A JP2004030924 A JP 2004030924A JP 2005221428 A JP2005221428 A JP 2005221428A
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- detection
- reducing gas
- solid electrolyte
- reference electrode
- 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.)
- Granted
Links
Abstract
Description
本発明は、固体電解質を用いた還元性ガス検知素子及び前記還元性ガス検知素子を用いた還元性ガス検知装置に関するものである。 The present invention relates to a reducing gas detection element using a solid electrolyte and a reducing gas detection device using the reducing gas detection element.
固体電解質を用いる電気化学式ガス検出素子は、一般に、固体電解質に検知極と対極とが一体に接合された構造からなり、その構成が全て固体からなるために、長期安定性にすぐれ、常温より高い温度で作動させる必要がある場合に特に好適である。また、このような検知素子は、その検知方式によって、電圧検出型と電流検出型とに分類される。 An electrochemical gas detection element using a solid electrolyte generally has a structure in which a detection electrode and a counter electrode are integrally joined to a solid electrolyte, and since the structure is all solid, it has excellent long-term stability and is higher than room temperature. It is particularly suitable when it is necessary to operate at temperature. Moreover, such a detection element is classified into a voltage detection type and a current detection type according to the detection method.
電圧検出型は、濃淡電池型ともいわれ、固体電解質の片面に検知極を、他面に対極をそれぞれ固着させ、検知極に未知濃度（分圧）の検知ガスを供給し、対極に既知濃度（分圧）の基準ガスを供給するとともに、これらのガスを互いに隔離すると、濃淡電池が形成され、その起電力を測定すれば、数１（１）に示すいわゆるネルンスト式にしたがって検知ガスの濃度（分圧）を知ることができるという原理にもとづくものである。 The voltage detection type is also called a concentration cell type. The detection electrode is fixed to one side of the solid electrolyte, the counter electrode is fixed to the other side, a detection gas having an unknown concentration (partial pressure) is supplied to the detection electrode, and a known concentration ( When a reference gas (partial pressure) is supplied and these gases are separated from each other, a concentration cell is formed. When the electromotive force is measured, the concentration of the detection gas (in accordance with the so-called Nernst equation shown in Equation (1)) This is based on the principle that the partial pressure can be known.
具体例としては、酸化物イオン導電性の安定化酸化ジルコニウムを固体電解質とし、空気を基準ガスとし、５００〜１０００℃で作動する酸素濃度検知素子がよく知られている。（特許文献１参照） As a specific example, an oxygen concentration detection element that operates at 500 to 1000 ° C. using oxide oxide conductive stabilized zirconium oxide as a solid electrolyte and air as a reference gas is well known. (See Patent Document 1)
電流検出型は、定電位電解型とも限界電流型ともいわれ、検知極と対極との間に、検知ガスの濃度に応じた限界電流が流れるように、一定電圧を印加した際に、検知極と対極との間に流れる電流を検出することによって、検知極に供給されるガスの濃度を検知するものである。具体例としては、安定化酸化ジルコニウムの片面に白金からなる検知極を、他面にやはり白金からなる対極をそれぞれ接合した素子の検知極側に、未知濃度の酸素含有ガスを供給し、一定の電圧を印加した際、化１（２）（３）式に示す反応が起こり、その際流れる電流から、検知ガスの酸素濃度を検知する方法が提案されている。 The current detection type is said to be a constant potential electrolysis type or a limit current type.When a constant voltage is applied between the detection electrode and the counter electrode so that a limit current corresponding to the concentration of the detection gas flows, The concentration of gas supplied to the detection electrode is detected by detecting the current flowing between the counter electrode and the counter electrode. As a specific example, an oxygen-containing gas having an unknown concentration is supplied to the detection electrode side of an element in which a detection electrode made of platinum is bonded to one side of stabilized zirconium oxide and a counter electrode made of platinum is bonded to the other side. When a voltage is applied, the reaction shown in the chemical formula 1 (2) and (3) occurs, and a method for detecting the oxygen concentration of the detection gas from the current flowing at that time has been proposed.
適用すべき固体電解質としては、通常は、検知ガス種に対応するイオンが伝導し得る材料を選択する必要がある。例えば、上記のように、検知ガスが酸素の場合には、酸化物イオン導電性の電解質が用いられ、検知ガスが水素の場合には、セリウム酸バリウム系あるいはセリウム酸ストロンチウム系などの水素イオン導電性の電解質が選択される。 As the solid electrolyte to be applied, it is usually necessary to select a material that can conduct ions corresponding to the detection gas species. For example, as described above, when the detection gas is oxygen, an oxide ion conductive electrolyte is used. When the detection gas is hydrogen, hydrogen ion conductivity such as barium cerate or strontium cerate is used. Sex electrolyte is selected.
検知ガスが水素及び各種炭化水素ガスなどの還元性ガスの場合には、上記のように、水素イオン導電性の固体電解質を用いるのが、従来必須であるとされていたが、水素イオン導電性のセリウム酸バリウム系あるいはセリウム酸ストロンチウム系電解質は、検知ガス雰囲気中に二酸化炭素が含まれる場合には、不安定であることに難点がある。 In the case where the detection gas is a reducing gas such as hydrogen and various hydrocarbon gases, as described above, it has conventionally been essential to use a hydrogen ion conductive solid electrolyte. These barium cerate-based or strontium cerate-based electrolytes have a drawback in that they are unstable when carbon dioxide is contained in the detection gas atmosphere.
また、検知素子を濃淡電池型とする際には、検知ガスと同一であって、しかも既知濃度の基準ガスを使用する必要があるが、このような措置は、実用上、極めて煩雑であり、現実的ではない。 In addition, when the sensing element is a concentration cell type, it is necessary to use a reference gas that is the same as the sensing gas and has a known concentration, but such a measure is practically extremely complicated, Not realistic.
さらには、固体電解質が一般に、高温でしか充分なイオン導電度を示さないという理由から、検知素子に、例えば白金抵抗体を接合し、この部分に電流を流すというような、温度制御が可能な加熱措置を施す必要があるが、従来のように、固体電解質の両面に検知極と対極を接合し、検知ガスと基準ガスとを固体電解質を介して隔離するという構造にした場合には、気密性を確保するための構造が複雑になるばかりか、加熱措置を施す余地が乏しくなる点も問題となっていた。 Furthermore, because the solid electrolyte generally exhibits sufficient ionic conductivity only at high temperatures, it is possible to control the temperature, for example, by bonding a platinum resistor to the sensing element and passing a current through this portion. Although it is necessary to take a heating measure, as in the conventional case, when the detection electrode and the counter electrode are joined to both sides of the solid electrolyte and the detection gas and the reference gas are isolated via the solid electrolyte, In addition to the complexity of the structure for ensuring safety, there is also a problem in that there is little room for heat treatment.
以上の理由から、例えば、溶融アルミニウム中の水素検出素子の如き特殊用途を除いた、一般用途向けに適した還元性ガス用固体電解質型検知素子は、未だに実用化されていない。 For the above reasons, for example, a solid oxide sensing element for reducing gas suitable for general use, excluding special uses such as a hydrogen sensing element in molten aluminum, has not been put into practical use.
上記実状に鑑み本発明の目的は、検知出力の安定性が高く、より簡単な構造で、しかも基準ガスを必要としない還元性ガス検出素子を提供することにある。 In view of the above circumstances, an object of the present invention is to provide a reducing gas detection element that has high detection output stability, a simpler structure, and does not require a reference gas.
本発明は、充分安定な酸化物イオン導電性固体電解質を適用するとともに、この固体電解質に検知極と対極を接合し、対極をガラス状ガス非透過性被膜で被覆することによって、基準ガスを特に用いなくても、還元性ガスの検知を可能にする構成の還元性ガス検知素子を提供するものである。さらには、このような固体電解質−電極接合体を、アルミナの如き絶縁性セラミック基板の片面に、他面に加熱用金属抵抗体を接合するという構造を採用することによって、還元性ガス検知装置をより小型化するものである。 The present invention applies a sufficiently stable oxide ion conductive solid electrolyte, joins a detection electrode and a counter electrode to the solid electrolyte, and coats the counter electrode with a glass-like gas-impermeable film, thereby making the reference gas particularly The present invention provides a reducing gas detection element having a configuration that enables detection of reducing gas even if it is not used. Further, by adopting a structure in which such a solid electrolyte-electrode assembly is joined to one surface of an insulating ceramic substrate such as alumina and a heating metal resistor is joined to the other surface, a reducing gas detection device is provided. The size is further reduced.
本発明は、水素、炭化水素ガス等の還元性ガスに適した固体電解質型検知素子について、実験を含めた検討を鋭意進めた結果得られた新しい知見に基づいてなされたものである。 The present invention has been made on the basis of new knowledge obtained as a result of diligent investigations including experiments on solid electrolyte type detection elements suitable for reducing gases such as hydrogen and hydrocarbon gases.
本発明にかかる還元性ガス検知素子の典型的模式構造を図１に示す。
１は、絶縁性セラミック基板であり、その材料としては、アルミナあるいはシリカ−アルミナ等が好適である。前記セラミック基板の片面に、酸化イットリウム（Ｙ２Ｏ３）もしくは酸化カルシウム（ＣａＯ）によって安定化された酸化ジルコニウム（ＺｒＯ２）からなる従来公知の酸化物イオン導電性の固体電解質２が一体に接合されている。固体電解質材料としては酸化セリウム（ＣｅＯ２）系でも良い。固体電解質の接合方法としては、ペレット状もしくはシート状固体電解質を従来公知のセラミック系接着材によって接着・加熱する方法あるいは固体電解質材料粉末としかるべき結合材とを混合したものを塗布・加熱する方法などが有効である。
A typical schematic structure of a reducing gas detecting element according to the present invention is shown in FIG.
Reference numeral 1 denotes an insulating ceramic substrate, and the material thereof is preferably alumina or silica-alumina. A conventionally known oxide ion conductive solid electrolyte 2 made of zirconium oxide (ZrO 2 ) stabilized by yttrium oxide (Y 2 O 3 ) or calcium oxide (CaO) is integrally joined to one surface of the ceramic substrate. Has been. The solid electrolyte material may be cerium oxide (CeO 2 ). As a solid electrolyte joining method, a method of adhering and heating a pellet-like or sheet-like solid electrolyte with a conventionally known ceramic adhesive, or a method of applying and heating a mixture of solid electrolyte material powder and an appropriate binder Etc. are effective.
固体電解質２の上には、検知極４及び対極（基準極）３が相互に隔離されるように、一体に接合されている。両電極とも、白金、パラジウム、ロジウム、ルテニウム、金などの貴金属もしくは、これらの貴金属の合金によって構成される。両電極ともスパッタリング法、ペースト法等当該分野で公知とされる方法によって接合される。対極（基準極）３は、ガス非透過性被覆層５によって被覆されている。このガス非透過性被覆層５の材料は、一般に市販されている、加熱によって溶融するガラス系材料が好適である。絶縁性セラミック基板１の固体電解質層２とは反対の面には、本検知素子の作動温度を維持するためのたとえば白金からなる加熱用金属抵抗体層６が、当該分野において公知のスパッタリング法、ペースト法等によって接合されている。加熱用金属抵抗体は、シート状とし、セラミック接着材により接着してもよい。 On the solid electrolyte 2, the detection electrode 4 and the counter electrode (reference electrode) 3 are integrally joined so as to be isolated from each other. Both electrodes are made of a noble metal such as platinum, palladium, rhodium, ruthenium, gold, or an alloy of these noble metals. Both electrodes are joined by a method known in the art such as a sputtering method or a paste method. The counter electrode (reference electrode) 3 is covered with a gas impermeable coating layer 5. The material of the gas impermeable coating layer 5 is preferably a glass-based material that is commercially available and melts by heating. On the surface opposite to the solid electrolyte layer 2 of the insulating ceramic substrate 1, a heating metal resistor layer 6 made of, for example, platinum for maintaining the operating temperature of the present sensing element is formed by a sputtering method known in the art, Joined by a paste method or the like. The heating metal resistor may be in the form of a sheet and bonded with a ceramic adhesive.
なお、上記のような各部材の接合構成あるいは接合順序については、さらに、さまざまな選択肢がある。まず、作動温度を高温にするために、外部加熱機構が別途に用意できる場合には、加熱用金属抵抗体を検知素子に一体接合しなくてもすむ。また、この場合には、絶縁性セラミック基板を用いなくて、固体電解質に検知極及び対極（基準極）を接合するとともに、対極（基準極）にガス非透過性被膜を被覆した接合体を製作し、この接合体を検知素子として、そのまま、使用することも可能である。さらには、この接合体を絶縁性セラミック基板に接合することも効果的である。一方、この接合体の製作にあたっては、固体電解質の同一面に検知極及び基準極を接合する（図１参照）のみならず、固体電解質の片面に検知極を、他面に対極（基準極）を接合する（図２参照）ことも有効な場合がある。なお、この接合体を絶縁性セラミック基板に接合する際、固体電解質の同一面に検知極及び対極（基準極）の双方を接合した型の場合には、固体電解質面と絶縁性セラミック基板とが隣り合うように接合するのに対し、固体電解質の片面に検知極を、他面に対極（基準極）を接合した型の場合には、検知極、固体電解質及び対極（基準極）のすべてが、絶縁性セラミック基板に隣り合う向きにして接合しなければならない。また、これら接合体を絶縁性セラミック基板に接合する際には、固体電解質−検知極−対極（基準極）の接合体を絶縁性セラミック基板に接合した後に、ガス非透過性被膜を対極（基準極）に被覆するという工程を選択した方が、対極（基準極）への検知ガスの接触を完全に防止するという観点からは、有利なことが多い。 In addition, there are various options for the joining configuration or joining order of each member as described above. First, if an external heating mechanism can be prepared separately to increase the operating temperature, the heating metal resistor need not be integrally joined to the sensing element. Also, in this case, without using an insulating ceramic substrate, a sensing electrode and a counter electrode (reference electrode) are bonded to the solid electrolyte, and a bonded body in which the counter electrode (reference electrode) is covered with a gas-impermeable film is manufactured. However, the joined body can be used as it is as a detection element. Furthermore, it is also effective to join this joined body to an insulating ceramic substrate. On the other hand, in the production of this joined body, not only the detection electrode and the reference electrode are joined to the same surface of the solid electrolyte (see FIG. 1), but also the detection electrode on one side of the solid electrolyte and the counter electrode (reference electrode) on the other surface. It may also be effective to join (see FIG. 2). When joining this bonded body to the insulating ceramic substrate, in the case of a type in which both the detection electrode and the counter electrode (reference electrode) are bonded to the same surface of the solid electrolyte, the solid electrolyte surface and the insulating ceramic substrate are In the case of a type in which the detection electrode is joined to one side of the solid electrolyte and the counter electrode (reference electrode) is joined to the other surface, the detection electrode, solid electrolyte, and counter electrode (reference electrode) are all connected. It must be bonded in the direction adjacent to the insulating ceramic substrate. When these assemblies are bonded to the insulating ceramic substrate, the solid electrolyte-detecting electrode-counter electrode (reference electrode) assembly is bonded to the insulating ceramic substrate, and then the gas non-permeable coating is applied to the counter electrode (reference electrode). It is often advantageous from the viewpoint of completely preventing the detection gas from contacting the counter electrode (reference electrode).
上記の構造からなる還元性ガス検知素子は、その全体が検知ガス雰囲気中におかれ、外部電源から、加熱用金属抵抗体６に電流を通すか、外部加熱機構によって、しかるべき作動温度（通常は４００〜６００℃）になるように加熱した上で、検知極と対極（基準極）との間の電圧を測定すると、その電圧と還元性検知ガス濃度の対数との間に直線性がみられる。換言すると、検知極−対極（基準極）電圧を測定することによって、還元性ガス濃度を検知することが可能となる。このガス検知素子によって、検知可能な還元性ガスは、水素、一酸化炭素、及びメタン、プロパン、ブタン等の炭化水素である。 The reducing gas detection element having the above structure is entirely placed in a detection gas atmosphere, and an appropriate operating temperature (usually normal current is passed from an external power source to the heating metal resistor 6 or by an external heating mechanism. When the voltage between the detection electrode and the counter electrode (reference electrode) is measured after heating to 400 to 600 ° C., there is linearity between the voltage and the logarithm of the reducing detection gas concentration. It is done. In other words, it is possible to detect the reducing gas concentration by measuring the detection electrode-counter electrode (reference electrode) voltage. Reducing gases that can be detected by this gas detection element are hydrogen, carbon monoxide, and hydrocarbons such as methane, propane, and butane.
本発明による検知素子の系は、従来の厳密な意味での濃淡電池系ではないので、前記（１）式のネルンスト式をそのまま適用することはできないために、その反応メカニズム及び検知メカニズムには不分明なところはある。
ひとつの推測としては、例えば、検知ガスとして水素を対象にし、検知極及び対極（基準極）として白金を用いた際には、検知極が、化２（４）式の平衡反応にもとづく水素濃度に応じた平衡電位を示し、対極（基準極）の表面において、酸素が吸着された形（Ｐｔ（Ｏ））になるために、対極（基準極）が、化２（５）式の平衡反応による平衡電位を示し、両極の平衡電位の差が電圧として検出されることが考えられる。
Since the sensing element system according to the present invention is not a conventional concentration battery system in the strict sense, the Nernst equation (1) cannot be applied as it is. There is an obvious place.
One presumption is that, for example, when hydrogen is used as the detection gas and platinum is used as the detection electrode and the counter electrode (reference electrode), the detection electrode has a hydrogen concentration based on the equilibrium reaction of Formula 2 (4). The equilibration potential according to the formula (2) is obtained because the counter electrode (reference electrode) is in a form in which oxygen is adsorbed on the surface of the counter electrode (reference electrode) (Pt (O)). It is conceivable that the difference between the equilibrium potentials of both electrodes is detected as a voltage.
以下、本発明の特長を述べる。
本発明によって、まず、検知ガスが水素、炭化水素等の還元性ガスであるにもかかわらず、固体電解質として、従来常識とされていたが、安定性に乏しい水素イオン導電体を用いる替わりに、より安定で、酸素濃度検出素子の分野では実用に供されている酸化物イオン導電体の適用が可能になり、検知素子としても安定性が向上する。また、検知極と対極（基準極）とを固体電解質に接合するとともに、対極（基準極）をガス非透過性被膜により被覆し、検知ガスと対極（基準極）との接触を防止することによって、特に基準ガスを用いることなく、検知ガスを検知素子全体に接触させても、検知ガスの検知を可能にしたことは、検知素子の構造をより簡単にするとともに、検知方法の簡易化をもたらす。さらには、加熱用金属抵抗体を検知素子に一体に接合した場合には、加熱機構を含めた検知装置の小型化を図ることが可能になる。
The features of the present invention will be described below.
According to the present invention, first, although the detection gas is a reducing gas such as hydrogen or hydrocarbon, it has been conventionally known as a solid electrolyte, but instead of using a hydrogen ion conductor with poor stability, Oxide ion conductors that are more stable and practically used in the field of oxygen concentration detection elements can be applied, and the stability of the detection elements is improved. In addition, the detection electrode and the counter electrode (reference electrode) are joined to the solid electrolyte, and the counter electrode (reference electrode) is covered with a gas-impermeable film to prevent contact between the detection gas and the counter electrode (reference electrode). In particular, the detection gas can be detected even when the detection gas is brought into contact with the entire detection element without using a reference gas, thereby making the structure of the detection element simpler and simplifying the detection method. . Furthermore, when the heating metal resistor is integrally joined to the detection element, it is possible to reduce the size of the detection device including the heating mechanism.
図２に示すように、まず、直径２５ｍｍ角、厚さ０．４ｍｍのイットリウム安定化酸化ジルコニウムからなる固体電解質の両面にスパッタリング法により、薄膜（１μｍ厚）の白金を固着させた。次に、この固体電解質−白金接合体を、レーザー加工機で切断し、横１．０ｍｍ、縦０．５ｍｍ、厚さ１．０ｍｍの寸法からなる複数の小片に切り出した。この小片において、白金の片方が検知極、他方が対極（基準極）となる。次に横１．５ｍｍ、縦２ｍｍ、厚さ０．４ｍｍの絶縁性アルミナ基板の片面に、検知極−固体電解質−対極（基準極）接合体の小片を、セラミック接着剤により接着した。次に、白金からなる検知極及び対極（基準極）の双方に、白金リード線をいわゆる白金ペーストによって接続した。次に、対極（基準極）のみをガラス系被覆材により被覆した。このガラス系被覆層がガス非透過性被覆層となる。次に、上記の絶縁性アルミナ基板の検知極−固体電解質−対極（基準極）接合面と反対の面に、加熱用白金抵抗体層をスパッタリング法により接合するとともに、その両端に白金リード線を取りつけた。かくして、還元性ガス検知素子が得られる。尚、スパッタリング法により得られた検知極及び対極は、多孔質で反応性の高いものとなっている。 As shown in FIG. 2, first, a thin film (1 μm thick) platinum was fixed to both surfaces of a solid electrolyte made of yttrium-stabilized zirconium oxide having a diameter of 25 mm square and a thickness of 0.4 mm by sputtering. Next, the solid electrolyte-platinum joined body was cut with a laser processing machine and cut into a plurality of small pieces having dimensions of 1.0 mm in width, 0.5 mm in length, and 1.0 mm in thickness. In this small piece, one of platinum serves as a detection electrode and the other serves as a counter electrode (reference electrode). Next, a small piece of a sensing electrode-solid electrolyte-counter electrode (reference electrode) assembly was adhered to one side of an insulating alumina substrate having a width of 1.5 mm, a length of 2 mm, and a thickness of 0.4 mm using a ceramic adhesive. Next, a platinum lead wire was connected to both a detection electrode and a counter electrode (reference electrode) made of platinum with a so-called platinum paste. Next, only the counter electrode (reference electrode) was covered with a glass-based coating material. This glass-based coating layer becomes a gas-impermeable coating layer. Next, a heating platinum resistor layer is joined to the surface opposite to the sensing electrode-solid electrolyte-counter electrode (reference electrode) joining surface of the insulating alumina substrate by sputtering, and platinum lead wires are attached to both ends thereof. I installed it. Thus, a reducing gas detection element is obtained. The detection electrode and the counter electrode obtained by the sputtering method are porous and highly reactive.
この還元性ガス検知素子を、加熱用金属抵抗体に外部電源から電流を流して、６００℃に保持するとともに、種々のガス種、濃度の雰囲気中に設置し、検知極と対極（基準極）との電圧（電位差）を測定したところ、図２に示す特性が得られた。すなわち、各種還元性ガス（水素、一酸化炭素、メタン、ブタン）に対して、その濃度（ｐｐｍ）の対数と検知極−対極（基準極）間電圧との間に、ほぼ直線的な関係が示された。また、この検知素子は、特に水素に対する感度が高いことが判明した。 This reducing gas detection element is supplied with current from an external power source to a heating metal resistor and maintained at 600 ° C., and is installed in atmospheres of various gas types and concentrations, and a detection electrode and a counter electrode (reference electrode) When the voltage (potential difference) was measured, the characteristics shown in FIG. 2 were obtained. That is, for various reducing gases (hydrogen, carbon monoxide, methane, butane), there is a substantially linear relationship between the logarithm of the concentration (ppm) and the voltage between the detection electrode and the counter electrode (reference electrode). Indicated. It was also found that this sensing element is particularly sensitive to hydrogen.
以上詳述するように、本発明は、より簡単な構造で、より簡便な方法による還元性ガスの検知を可能にするガス検知素子及びガス検出装置を提供するものであり、その工業的価値、極めて大である。 As described above in detail, the present invention provides a gas detection element and a gas detection device that enable detection of reducing gas by a simpler method with a simpler structure, and its industrial value. It is extremely large.
１ 絶縁基板
２ 固体電解質
３ 基準極
４ 検知極
５ ガス非透過性被膜
６ 加熱機構
1 Insulating substrate 2 Solid electrolyte 3 Reference electrode 4 Detection electrode 5 Gas impermeable coating 6 Heating mechanism
Claims (9)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004030924A JP4532923B2 (en) | 2004-02-06 | 2004-02-06 | Reducing gas detection element and reducing gas detection device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004030924A JP4532923B2 (en) | 2004-02-06 | 2004-02-06 | Reducing gas detection element and reducing gas detection device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2005221428A true JP2005221428A (en) | 2005-08-18 |
| JP4532923B2 JP4532923B2 (en) | 2010-08-25 |
Family
ID=34997177
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2004030924A Expired - Fee Related JP4532923B2 (en) | 2004-02-06 | 2004-02-06 | Reducing gas detection element and reducing gas detection device |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4532923B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007248335A (en) * | 2006-03-17 | 2007-09-27 | New Industry Research Organization | Reducible gas sensor |
| JP2007248334A (en) * | 2006-03-17 | 2007-09-27 | New Industry Research Organization | Reducible gas sensor and its manufacturing method |
| US9952175B2 (en) | 2014-06-09 | 2018-04-24 | Fujitsu Limited | Gas sensor and sensor device |
| US10481146B2 (en) | 2015-05-22 | 2019-11-19 | Fujitsu Limited | Gas sensor and information processing system |
| US10670552B2 (en) | 2014-06-09 | 2020-06-02 | Fujitsu Limited | Gas sensor and sensor device |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10503022A (en) * | 1994-07-28 | 1998-03-17 | ロト テヒニク ゲーエムベーハー ウント コー フォルシュンク フュア アウトモビル ウント ウンベルトテヒニク | Solid electrolyte sensor for measuring gaseous anhydride. |
| JP2001194337A (en) * | 2000-01-07 | 2001-07-19 | Tokuyama Corp | Method for measuring gas concentration |
| JP2003107001A (en) * | 2001-09-28 | 2003-04-09 | Matsushita Electric Ind Co Ltd | Composite sensor |
| JP2003107110A (en) * | 2001-09-28 | 2003-04-09 | Toshiba Corp | Electric field measuring sensor and its manufacturing method |
-
2004
- 2004-02-06 JP JP2004030924A patent/JP4532923B2/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10503022A (en) * | 1994-07-28 | 1998-03-17 | ロト テヒニク ゲーエムベーハー ウント コー フォルシュンク フュア アウトモビル ウント ウンベルトテヒニク | Solid electrolyte sensor for measuring gaseous anhydride. |
| JP2001194337A (en) * | 2000-01-07 | 2001-07-19 | Tokuyama Corp | Method for measuring gas concentration |
| JP2003107001A (en) * | 2001-09-28 | 2003-04-09 | Matsushita Electric Ind Co Ltd | Composite sensor |
| JP2003107110A (en) * | 2001-09-28 | 2003-04-09 | Toshiba Corp | Electric field measuring sensor and its manufacturing method |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007248335A (en) * | 2006-03-17 | 2007-09-27 | New Industry Research Organization | Reducible gas sensor |
| JP2007248334A (en) * | 2006-03-17 | 2007-09-27 | New Industry Research Organization | Reducible gas sensor and its manufacturing method |
| US9952175B2 (en) | 2014-06-09 | 2018-04-24 | Fujitsu Limited | Gas sensor and sensor device |
| US10670552B2 (en) | 2014-06-09 | 2020-06-02 | Fujitsu Limited | Gas sensor and sensor device |
| US10481146B2 (en) | 2015-05-22 | 2019-11-19 | Fujitsu Limited | Gas sensor and information processing system |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4532923B2 (en) | 2010-08-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3871497B2 (en) | Gas sensor | |
| JP3311218B2 (en) | Hydrocarbon sensor | |
| US7235171B2 (en) | Hydrogen sensor, hydrogen sensor device and method of detecting hydrogen concentration | |
| KR101052618B1 (en) | Nitrogen oxide gas sensor with long term signal stability | |
| EP1635171B1 (en) | Hydrocarbon sensor | |
| JPH09274011A (en) | Nitrogen oxide detector | |
| JP4783095B2 (en) | Hydrogen gas detection element and hydrogen gas detection device | |
| WO2015002060A1 (en) | Co sensor and method for manufacturing co sensor | |
| JP4532923B2 (en) | Reducing gas detection element and reducing gas detection device | |
| US9599598B2 (en) | SOx gas sensor and method of measuring concentration of SOx gas | |
| KR101052617B1 (en) | Nitrogen Oxide Gas Sensor | |
| JP4465677B2 (en) | Hydrogen gas detector | |
| JPH10123093A (en) | Solid electrolytic hydrogen sensor | |
| JP2006133039A (en) | Nitrogen oxide sensor | |
| JP2000028573A (en) | Hydrocarbon gas sensor | |
| KR101133267B1 (en) | NOx gas sensor | |
| JP2008267845A (en) | Gas sensor | |
| JP2007278876A (en) | Hydrogen sensor | |
| JP4904238B2 (en) | Gas sensor and gas detection device | |
| US10161899B2 (en) | Oxygen sensor with electrochemical protection mode | |
| JP4912968B2 (en) | Non-methane hydrocarbon gas detector | |
| JP4271053B2 (en) | Carbon dioxide detector | |
| JP5339754B2 (en) | Oxygen gas concentration measurement method | |
| KR101436358B1 (en) | NOx gas sensor | |
| Guth | Potentiometric CO2 Sensors with Solid Electrolyte |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20061206 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20090407 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20090423 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20090622 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20091203 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20100201 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20100513 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20100611 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 Ref document number: 4532923 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130618 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140618 Year of fee payment: 4 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |