JPS62200257A - Proton conductor atmosphere detector - Google Patents
Proton conductor atmosphere detectorInfo
- Publication number
- JPS62200257A JPS62200257A JP61043743A JP4374386A JPS62200257A JP S62200257 A JPS62200257 A JP S62200257A JP 61043743 A JP61043743 A JP 61043743A JP 4374386 A JP4374386 A JP 4374386A JP S62200257 A JPS62200257 A JP S62200257A
- Authority
- JP
- Japan
- Prior art keywords
- proton conductor
- activated carbon
- ammonia
- basic gas
- atmosphere
- 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
- 239000004020 conductor Substances 0.000 title claims abstract description 45
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000002250 absorbent Substances 0.000 claims abstract description 11
- 230000002745 absorbent Effects 0.000 claims abstract description 11
- 230000006866 deterioration Effects 0.000 claims abstract description 8
- 238000001514 detection method Methods 0.000 claims description 20
- 239000000126 substance Substances 0.000 claims description 15
- 230000002378 acidificating effect Effects 0.000 claims description 11
- 239000004480 active ingredient Substances 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 61
- 229910021529 ammonia Inorganic materials 0.000 abstract description 30
- 230000000694 effects Effects 0.000 abstract description 14
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 abstract description 10
- 239000002253 acid Chemical class 0.000 abstract description 8
- 150000003839 salts Chemical class 0.000 abstract description 8
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 36
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- KIQKNTIOWITBBA-UHFFFAOYSA-K antimony(3+);phosphate Chemical compound [Sb+3].[O-]P([O-])([O-])=O KIQKNTIOWITBBA-UHFFFAOYSA-K 0.000 description 11
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 9
- 229910000365 copper sulfate Inorganic materials 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 6
- AQTIRDJOWSATJB-UHFFFAOYSA-K antimonic acid Chemical compound O[Sb](O)(O)=O AQTIRDJOWSATJB-UHFFFAOYSA-K 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 125000003172 aldehyde group Chemical group 0.000 description 2
- -1 amine compounds Chemical class 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 2
- 229940044175 cobalt sulfate Drugs 0.000 description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 2
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- WWILHZQYNPQALT-UHFFFAOYSA-N 2-methyl-2-morpholin-4-ylpropanal Chemical compound O=CC(C)(C)N1CCOCC1 WWILHZQYNPQALT-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000005955 Ferric phosphate Substances 0.000 description 1
- 229910002340 LaNiO3 Inorganic materials 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 238000010669 acid-base reaction Methods 0.000 description 1
- 150000008043 acidic salts Chemical class 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- CMMUKUYEPRGBFB-UHFFFAOYSA-L dichromic acid Chemical compound O[Cr](=O)(=O)O[Cr](O)(=O)=O CMMUKUYEPRGBFB-UHFFFAOYSA-L 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- 229940116007 ferrous phosphate Drugs 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 229910000155 iron(II) phosphate Inorganic materials 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- SDEKDNPYZOERBP-UHFFFAOYSA-H iron(ii) phosphate Chemical compound [Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SDEKDNPYZOERBP-UHFFFAOYSA-H 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Landscapes
- Measuring Oxygen Concentration In Cells (AREA)
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
Abstract
Description
【発明の詳細な説明】
［発明の利用分野］
この発明は、プロトン導電体の起電力や内部抵抗から、
水素や一酸化炭素等のガスや水蒸気を検出する装置に関
する。この発明はより詳細には、この種の装置における
、アンモニアやアミン化合物、あるいはヒドラジン等の
塩基性ガスでのプロトン導電体の劣化の防止に関する。[Detailed Description of the Invention] [Field of Application of the Invention] This invention is based on the electromotive force and internal resistance of a proton conductor.
This invention relates to a device that detects gases such as hydrogen and carbon monoxide, and water vapor. More particularly, the present invention relates to preventing deterioration of proton conductors in this type of device due to ammonia, amine compounds, or basic gases such as hydrazine.
［従来技術］
プロトン導電体は、水素や一酸化炭素等へのセンサ、あ
るいは湿度へのセンサとして利用することができる。水
素や一酸化炭素へのセンサとしては、プロトン導電体本
来の性質を生かし、その起電力から検出を行うことがで
きる（特開昭６０−７３５８号）。この場合の問題は起
電力がガス濃度の対数に比例することに有り、発明者ら
はガス濃度に直接比例した出力を得ろため２つの技術を
開発した。第１のものでは、導電体に一対の電極を接続
してこれらの電極を短絡し、別に一対の電極を導電体に
接続１．て導電体の内部起電力を測定ずろ。短絡電流は
ガス濃度に比例するが、湿度の影響を受ける。一方円部
起電力は、ガス濃度に比例しかつ湿度の影響がほとんど
ない（特願昭６１−１５，２２２号）。第２のものでは
、導電体の内部抵抗を測定して、内部抵抗と短絡電流と
の積を出力として取り出す。短絡電流の湿度依存性と内
部抵抗の湿度依存性とは逆向きでほぼ等しく、これらの
積を用いることによりガス濃度に比例し湿度の影響の小
さい出力が得られろ（特願昭６１−１５．２２３号）。[Prior Art] A proton conductor can be used as a sensor for hydrogen, carbon monoxide, etc., or as a sensor for humidity. As a sensor for hydrogen or carbon monoxide, it is possible to make use of the inherent properties of proton conductors and perform detection from their electromotive force (Japanese Patent Application Laid-Open No. 60-7358). The problem in this case is that the electromotive force is proportional to the logarithm of the gas concentration, and the inventors have developed two techniques to obtain an output that is directly proportional to the gas concentration. The first one involves connecting a pair of electrodes to a conductor and shorting these electrodes, and connecting another pair of electrodes to the conductor. Measure the internal electromotive force of the conductor. Short circuit current is proportional to gas concentration, but is affected by humidity. On the other hand, the circular electromotive force is proportional to the gas concentration and is hardly affected by humidity (Japanese Patent Application No. 15, 1988, 222). In the second one, the internal resistance of the conductor is measured and the product of the internal resistance and the short circuit current is taken as an output. The humidity dependence of the short-circuit current and the humidity dependence of the internal resistance are almost equal in opposite directions, and by using the product of these, it is possible to obtain an output that is proportional to the gas concentration and is less affected by humidity. .223).
発明者らはまた、プロトン導電体の内部抵抗から湿度を
検出し得ることを見出だした。この場合の課題は、内部
抵抗が湿度により大きく変化する材ｆ１を探求すること
に有る。発明者らは、リン酸アンチモン・ＨＳｂＰ、Ｏ
ａ（特願昭６１−１５．２２１号）や、リン酸シリカ弓
−１２ＳｉＰ、Ｏｓ（出願人の本日付（）の特許出願（
１））が好ましい物質であることを見出だした。The inventors have also discovered that humidity can be detected from the internal resistance of the proton conductor. The problem in this case is to find a material f1 whose internal resistance changes greatly depending on humidity. The inventors discovered that antimony phosphate/HSbP, O
a (Japanese Patent Application No. 15.221/1982), Silica Phosphate Bow-12SiP, Os (patent application filed by the applicant today ())
It has been found that 1)) is a preferred material.
ところで、発明者らは、プロトン導電体がアンモニアや
、ヒドラジン、あるいはメチルアミン、プロピルアミン
等の各種アミン類により劣化することを見出たした。こ
れらのものはいずれも塩Ｊ１１８性のアミノ化合物であ
り、低沸点で容易に気化ずろ化合物である。プロトン導
電体は一般にギヤリアーとしてプロトンを含んでいる。By the way, the inventors have discovered that proton conductors are degraded by ammonia, hydrazine, and various amines such as methylamine and propylamine. All of these compounds are amino compounds with salt J118 properties, and have low boiling points and easily vaporize. Proton conductors generally contain protons as a gear.
このことはプロトン導電体が酸性物質であることを意味
する。This means that the proton conductor is an acidic substance.
ここで導電体がアンモニア等の塩基性ガスと接触すると
、アンモニアとプ［１トンとが反応しアンモニウム塩が
生ずる。生成したアンモニウム塩は安定で、４００℃程
度で熱処理を行わない限り、脱離も分解もしない。この
ためプロトン導電体の起電力や内部抵抗は、塩基性ガス
により変化する。Here, when the conductor comes into contact with a basic gas such as ammonia, ammonia and phosphorus react to form an ammonium salt. The produced ammonium salt is stable and will not be desorbed or decomposed unless heat treated at about 400°C. Therefore, the electromotive force and internal resistance of the proton conductor change depending on the basic gas.
［発明の課題］
この発明は、アンモニア等の塩基性ガスによる劣化を防
止し、プロトン導電体を用いた雰囲気の検出装置の信頼
性を向−１−させることを課題とする。[Problems of the Invention] An object of the present invention is to prevent deterioration caused by basic gases such as ammonia and to improve the reliability of an atmosphere detection device using a proton conductor.
［発明の構成と機能］
この発明は、プロトン導電体雰囲気センサを用いた雰囲
気の検出装置において、塩基性ガス吸収剤を有効成分と
するフィルターを設けてアンモニア等の塩基性ガスを除
去し、プロトン導電体の劣化を防止することを特徴とす
る。なおここにプロトン導電体とは、プロトンが主たる
キャリアーである導電体を意味する。[Structure and Function of the Invention] The present invention provides an atmosphere detection device using a proton conductor atmosphere sensor, in which a filter containing a basic gas absorbent as an active ingredient is provided to remove basic gases such as ammonia, and to detect protons. It is characterized by preventing deterioration of the conductor. Note that the proton conductor herein means a conductor in which protons are the main carrier.
塩基性ガス吸収剤はアンモニア等のガスを除去し得ろも
ので育れば良く、吸着剤を用いることもでき、また酸塩
基反応を利用して酸性物質を用いろこともできる。次に
実施」二の問題として、湿度の検出の場合、吸収剤によ
る水蒸気分圧の変化を避ける必要が有る。このため水溶
液や潮解性物質は好ましくない。一方ガスの検出の場合
はこれらの制限はなく、希硫酸等の水溶液や５酸化リン
等の潮解性物質でも用いることができる。吸収剤として
好ましいものの１つは活性炭である。しかし活性炭のア
ンモニア吸着活性は高くはないので、４一
種々の改質を施すのが良い。例えば活性炭を液相中等で
部分的に酸化すると、表面に生ずろ水酸基やアセデル基
、アルデヒド基等のたぬに活性炭の極性が増し、アンモ
ニア等の吸着活性を飛躍的に高めることができる。次に
活性炭を濃硫酸等で処理し、部分的にスルホン化しても
良い。また活性炭に硫酸銅・ＣｌｌＳＯ４・５Ｈ２０や
、硫酸コバルトＣＯ３Ｏ４・ｎＨｚｏ等の酸性物質を添
加しても良い。これらの場合は活性炭の吸着作用とスル
ポン酸や硫酸銅等の酸性物質との相乗作用により、塩基
性ガスへの吸着活性は著しく向」二する。そして一端吸
着したガスは酸と反応して固定され、活性炭から脱離し
ない。The basic gas absorbent may be anything that can remove gas such as ammonia, an adsorbent may be used, or an acidic substance may be used by utilizing an acid-base reaction. Next, the second problem is that when detecting humidity, it is necessary to avoid changes in the water vapor partial pressure caused by the absorbent. For this reason, aqueous solutions and deliquescent substances are not preferred. On the other hand, in the case of gas detection, these limitations do not apply, and aqueous solutions such as dilute sulfuric acid and deliquescent substances such as phosphorus pentoxide can also be used. One of the preferred absorbents is activated carbon. However, since the ammonia adsorption activity of activated carbon is not high, it is better to perform one of the four types of modification. For example, when activated carbon is partially oxidized in a liquid phase, etc., the polarity of the activated carbon increases due to the formation of hydroxyl groups, acedel groups, aldehyde groups, etc. on the surface, and the adsorption activity of ammonia etc. can be dramatically increased. Next, the activated carbon may be partially sulfonated by treating it with concentrated sulfuric acid or the like. Further, an acidic substance such as copper sulfate/CllSO4/5H20 or cobalt sulfate CO3O4/nHzo may be added to the activated carbon. In these cases, the adsorption activity for basic gases is significantly improved due to the synergistic effect of the adsorption action of activated carbon and acidic substances such as sulfonic acid and copper sulfate. The adsorbed gas reacts with the acid and becomes fixed, and does not desorb from the activated carbon.
吸収剤には、硫酸銅や硫酸コバルト、硫酸アルミニウム
・ＡＩ、（Ｓｏ、）３・１８Ｈ２０、硫酸水素アンモニ
ウム・Ｎ Ｈ４・Ｈ８Ｏいリン酸第１鉄・Ｆ ｅ３（Ｐ
ｏ＋）ｔ ” ８ ＨｔＯ、リン酸第２鉄・ＦｅＰＯ
４・２Ｈ２０等の酸性物質を用いても良い。これらのも
のは潮解性のない酸性塩であり、湿度検出の妨げになら
ない。これらのものは単味で用いても良いが、紙や多孔
質のプラスチック、多孔質陶器等に担持させて用いても
良い。もち論これらの酸性塩は活性炭に担持させても良
い。なおここでは酸性塩に付いて代表的な水和物の組成
を示したが、永和肴は種々変化するので、これに限るも
のではない。Absorbents include copper sulfate, cobalt sulfate, aluminum sulfate/AI, (So,)3/18H20, ammonium hydrogen sulfate/NH4/H8O, ferrous phosphate/Fe3(P), etc.
o+)t” 8 HtO, ferric phosphate/FePO
An acidic substance such as 4.2H20 may also be used. These are non-deliquescent acid salts and do not interfere with humidity detection. These materials may be used alone, or may be supported on paper, porous plastic, porous ceramics, or the like. Of course, these acid salts may be supported on activated carbon. Although the composition of typical hydrates of acid salts has been shown here, the composition is not limited to this, as Eiwa appetizers vary in various ways.
ガスの検出の場合、吸湿性や潮解性等の制限かないので
、ノリ力ゲルやγ−アルミナ等の吸湿性の吸着媒、より
好ましくはこれらに酸性物質を添加したもの、希硫酸や
希リン酸等の酸性水溶液、さらに５酸化リン、リン酸二
水素カリウム・Ｋ−Ｈ３ＰＯ，等の潮解性の固体の酸性
物質も用いろことができる。In the case of gas detection, there are no restrictions on hygroscopicity or deliquescent properties, so hygroscopic adsorbents such as glue gel and γ-alumina, more preferably those with acidic substances added, dilute sulfuric acid or dilute phosphoric acid, are used. Further, deliquescent solid acidic substances such as phosphorus pentoxide, potassium dihydrogen phosphate/K-H3PO, etc. can also be used.
この発明の検出装置は、相対湿度や絶対湿度の検出に用
いることができろ。またこの発明の検出装置は、水素や
一酸化炭素、あるいは容易？こ分解して水素を発生させ
ろ物質の検出に用いることができる。The detection device of this invention can be used to detect relative humidity and absolute humidity. Also, the detection device of this invention can detect hydrogen, carbon monoxide, or easily? This can be used to detect substances that are decomposed to generate hydrogen.
［実施例］
（試料の調整）
湿度の検出用材料として、リン酸アンチモン（ＨＳｈＰ
２０ｓ）を合成した。塩化アンチモン（Ｓ ｂＣ１５）
を１０倍のモル量の濃リン酸（８３Ｐ０４８５ｗｔ％）
中に滴下し、撹はん下で２７０℃にて２４時間反応させ
る。この反応によりリン酸アンチモンを主とずろ白色固
体が生成ずろ。生成物を分離し、再一度アンチモンと等
モル量のリン酸を加え、２４０℃に４日間加熱し反応を
完了させる。[Example] (Sample preparation) Antimony phosphate (HShP) was used as a humidity detection material.
20s) was synthesized. Antimony chloride (S bC15)
10 times the molar amount of concentrated phosphoric acid (83P0485wt%)
and reacted at 270° C. for 24 hours with stirring. This reaction produces a white solid consisting mainly of antimony phosphate. The product is separated, antimony and equimolar amounts of phosphoric acid are added once again, and the reaction is completed by heating to 240° C. for 4 days.
生成物をろ過し、Ｐ Ｆｌが６になるまで水を加えて遠
心分離を繰り返し、過剰のリン酸等を除去する。The product is filtered, water is added until P Fl becomes 6, and centrifugation is repeated to remove excess phosphoric acid, etc.
得られるリン酸アンチモンは白色の固体である。The resulting antimony phosphate is a white solid.
次に同じく湿度の検出用材料として、リン酸シリカ（Ｈ
２ＳｉＰｚＯｅ）を合成した。テトラエトキンシリケイ
ト（Ｓ ｌ（ＯＣｐＨ５）Ｊを、リン酸と水とで、１：
１５：１５のモル比で混合・撹拌し、塩酸を滴下してゲ
ル状の化合物とする。反応液をそのまま１５０℃に１５
時間保った後、アセトンで洗浄してリン酸ソリ力を得た
。Next, phosphoric acid silica (H
2SiPzOe) was synthesized. Tetraethquin silicate (Sl(OCpH5)J) was prepared with phosphoric acid and water at 1:
Mix and stir at a molar ratio of 15:15, and add hydrochloric acid dropwise to form a gel-like compound. The reaction solution was heated to 150℃ for 15 minutes.
After keeping it for a while, it was washed with acetone to obtain phosphoric acid solubility.
リン酸アンチモンやリン酸シリカは、チロらにより発見
された化合物であるが（Ｅ、 Ｔｈ１ｒｏ ｅｔ。Antimony phosphate and silica phosphate are compounds discovered by Thiro et al.
ａｌ 無機・一般化学誌 Ｚｅｉｔｓｃｈｒｉｒｔ
ｒｕｒ Ａｎ −ｏｒｇａｎｉｓｈｅ ｕｎｄ Ａ Ｉ
ｌｇｅｍｅｉｎ Ｃｈｅｍｉｅ ３４６巻９２頁 １９
６６年）、その性状に付いてはほとんど知られていない
。ここではＸ線回折から化合物を同定すると共に、輸率
の測定等からプロトン導電体であることを確認した。al Inorganic/General Chemistry Journal Zeitsschirt
rur An-organishe und A I
lgemein Chemie volume 346 page 92 19
(1966), but little is known about its properties. Here, the compound was identified from X-ray diffraction and confirmed to be a proton conductor by measurements of the transfer number.
水素や一酸化炭素の検出用材料として、アンチモン酸（
Ｓｂｔ０５” ｎＦｒｔｏ、ｎは２程度）を用いた。Antimonic acid (
Sbt05''nFrto, n is about 2) was used.
この化合物はプロトン導電体として知られており（例え
ば特開昭６０−７３５８号）、酸化アンチモン（Ｓｂ２
０３）と１５倍当量の過酸化水素との反応から調整した
。This compound is known as a proton conductor (for example, JP-A-60-7358), and antimony oxide (Sb2
03) and 15 equivalents of hydrogen peroxide.
（塩基性ガス吸収フィルター）
フィルターにはアンモニア等の塩基性ガスを吸収するも
のであれば任意のものを用いることが出来るが、好まし
いものは活性炭を改質してアンモニア吸収活性を高めた
ものや、硫酸銅等の酸性塩である。(Basic gas absorption filter) Any filter can be used as long as it absorbs basic gases such as ammonia, but preferred ones are activated carbon modified to increase ammonia absorption activity, and filters that absorb basic gases such as ammonia. , copper sulfate, and other acid salts.
ここではフィルターとして以下のものを用いた。The following filters were used here.
ａ）活性炭フィルター： 直径約４ ｍｍ、長さ５ｍｍ
程度の円筒形の活性炭で気体吸着用のもの。なお使用量
はセンサ１個当たり約１ｇである。a) Activated carbon filter: Approximately 4 mm in diameter and 5 mm in length
A cylindrical activated carbon for gas adsorption. The amount used is approximately 1 g per sensor.
ｂ）スルポン化活性炭：」二記の活性炭を８０℃の濃混
酸中でスルホン化し、アンモニア吸着活性を高めたもの
。この処理で生じたスルポン酸基のため、アンモニアの
吸着活性が高まる。b) Sulfonated activated carbon: sulfonated activated carbon described in 2 above in a concentrated mixed acid at 80°C to increase its ammonia adsorption activity. Due to the sulfonic acid groups generated in this treatment, the ammonia adsorption activity increases.
Ｃ）部分酸化活性炭：ａ）の活性炭を８０℃の重クロム
酸中で液相酸化したもの。活性炭の表面にアルデヒド基
やケトン基、水酸基、アセチル基等が生成し、アンモニ
ア吸着活性が増す。C) Partially oxidized activated carbon: The activated carbon of a) is oxidized in a liquid phase in dichromic acid at 80°C. Aldehyde groups, ketone groups, hydroxyl groups, acetyl groups, etc. are generated on the surface of activated carbon, increasing the ammonia adsorption activity.
ｄ）酸性物質を担持させた活性炭： 硫酸銅等の酸性物
質を活性炭に担持させたもので、ここでは無水塩に換算
して活性炭１ｇ当たり５０ｍｇの硫酸銅を添加したもの
を用いた。d) Activated carbon supporting an acidic substance: Activated carbon supports an acidic substance such as copper sulfate, and in this case, 50 mg of copper sulfate was added per 1 g of activated carbon in terms of anhydrous salt.
ｅ）酸性塩； 連続気泡の発泡ポリウレタンにセンサ１
個当たり５０ｍｇの硫酸銅を添加したもの。e) Acidic salt; sensor 1 in open-cell foamed polyurethane
Added 50mg of copper sulfate per piece.
（湿度の検出装置）
第１図において、（２）はプロトン導電体湿度センサで
、（４）はリン酸アンチモンやリン酸ソリ力等のプロト
ン導電体の成型体である。（６）、（８）は電極で、白
金やバラディラム等の貴金属の粉末やＬａＮｉＯ３等の
金属酸化物を用いろ。（１０）はプロトン導電体（４）
を一定温度に加熱するためのヒータで、設（」なくとも
良い。（１２）は適宜のハウジング、（１４）は塩基性
ガスの吸収フィルター、（１６）、（Ｉ８）はナイロン
等のメッシュである。(Humidity Detection Apparatus) In FIG. 1, (2) is a proton conductor humidity sensor, and (4) is a molded body of a proton conductor such as antimony phosphate or phosphate silicate. (6) and (8) are electrodes, and use noble metal powder such as platinum or valadilum or metal oxide such as LaNiO3. (10) is a proton conductor (4)
(12) is a suitable housing, (14) is a basic gas absorption filter, (16) and (I8) are meshes made of nylon, etc. be.
フィルター（１４）は図示のにうにセンサ（２）と一体
としても良いが、センサ（２）と分離し、自由に交換し
得るようにしても良い。The filter (14) may be integrated with the sensor (2) as shown, but it may also be separated from the sensor (2) so that it can be replaced freely.
ヒータ（１０）には端子０１１）、ＣＨ２）を介して、
ヒータ電源（２０）を接続する。また電極（６）、（８
）には、端子（Ｓｌ）、（Ｓ２）を介し、例えば２００
Ｈｚの交流電源（２２）とインピーダンス検出用の抵抗
（２４）とを接続し、抵抗（２４）への電圧からセンサ
（２）のインピーダンスを測定する。The heater (10) is connected via terminals 011) and CH2).
Connect the heater power source (20). Also, electrodes (6), (8
) through terminals (Sl) and (S2), for example, 200
A Hz AC power source (22) and a resistor (24) for impedance detection are connected, and the impedance of the sensor (2) is measured from the voltage applied to the resistor (24).
実際には電源（２２）は直流でも良いが、水素の存在に
よる起電力を避け、過電圧の印加による電極や導電体（
４）の劣化を避けるため、交流が好ましい。In reality, the power source (22) may be a direct current, but it is important to avoid electromotive force due to the presence of hydrogen, and to prevent the electrodes and conductors from applying overvoltage.
In order to avoid the deterioration of 4), alternating current is preferable.
第２図に各温度でのリン酸アンチモンの感湿特性を示す
。図から明らかなように、内部抵抗は湿度により著しく
変化する。Figure 2 shows the moisture sensitivity characteristics of antimony phosphate at various temperatures. As is clear from the figure, the internal resistance changes significantly depending on the humidity.
第３図に３００ ｐｐｍのアンモニアによる、リン酸ア
ンチモンの高抵抗化の状況を示す。アンモニアとの接触
時間は１時間で、接触後４時間の特性を示す。またセン
サ温度は１５０°Ｃで、結果は５個のセンサの平均であ
る。接触前のｌ０Ｔｏｒｒの水蒸気中での抵抗値を基準
とすると、フィルター（１４）を設けないものでは抵抗
値は２倍程度増大する。未処理の活性炭をそのまま用い
たものでも高抵抗化を抑制し得るが、効果は小さい。こ
れに対して、スルポン化活性炭や硫酸銅をポリウレタン
に加えたものでは、抵抗値はほとんど変化していない。FIG. 3 shows how the resistance of antimony phosphate increases due to 300 ppm of ammonia. The contact time with ammonia was 1 hour, and the characteristics were shown for 4 hours after contact. Also, the sensor temperature was 150°C, and the results are the average of 5 sensors. Based on the resistance value in water vapor of 10 Torr before contact, the resistance value increases about twice in the case where the filter (14) is not provided. Using untreated activated carbon as is can also suppress the increase in resistance, but the effect is small. On the other hand, when sulfonated activated carbon or copper sulfate is added to polyurethane, the resistance value hardly changes.
第４図に、リン酸シリカの導電率と各温度での相対湿度
との関係を示す。８０〜２００℃程度の範囲で、導電率
は湿度により大きく変化する。FIG. 4 shows the relationship between the electrical conductivity of phosphoric acid silica and the relative humidity at each temperature. In the range of about 80 to 200°C, the electrical conductivity changes greatly depending on the humidity.
第５図に、３００ｐｐｍのアンモニアによるリン酸シリ
カの抵抗変化を示す。測定条件は、第３図の場合と同様
で、センサ温度は１５０℃である。FIG. 5 shows the resistance change of phosphoric acid silica due to 300 ppm of ammonia. The measurement conditions were the same as in the case of FIG. 3, and the sensor temperature was 150°C.
フィルターなしのものではアンモニアにより抵抗値は３
倍程度増大するが、フィルターによりこの変化を防止す
ることができる。また単味の活性炭に比べ、スルポン化
等の処理を施した活性炭や酸性塩等が好ましいことも同
様である。In the case without a filter, the resistance value is 3 due to ammonia.
Although it increases by about twice as much, this change can be prevented by using a filter. Similarly, activated carbon treated with sulfonation, acid salts, etc. are preferable to plain activated carbon.
第６図に、１０５℃でのアンチモン酸のアンモニアにに
る抵抗変化を示す。測定条件は第３図の場合と同様で、
処理前のｌ０Ｔｏｒｒの水蒸気中での抵抗値は約１００
にΩであった。アンモニアとの接触により高抵抗化する
こと、活性炭等のフィルターによりアンモニアの影響を
除けることは同じである。しかし湿度への感度は、リン
酸アンチモンやリン酸シリカに比べ低い。これはアンチ
モン酸の感湿特性が低いというよりも、リン酸アンチモ
ンやリン酸シリカの感湿特性が極めて高いためである。FIG. 6 shows the resistance change of antimonic acid to ammonia at 105°C. The measurement conditions are the same as in Figure 3.
The resistance value in water vapor of 10 Torr before treatment is approximately 100
It was Ω. It is the same that the resistance increases due to contact with ammonia, and that the influence of ammonia is removed using a filter such as activated carbon. However, its sensitivity to humidity is lower than that of antimony phosphate and silica phosphate. This is not because antimonic acid has low moisture sensitivity, but rather because antimony phosphate and phosphoric silica have extremely high moisture sensitivity.
このような効果はアンモニアでのみ生ずるのではなく、
ヒドラジンやメチルアミン、ジエヂルアミン等の他の塩
基性ガスでも同様に生ずる。またその効果は一時的なも
のではなく、長期間回復しない。さらにフィルター（１
４）には、−１−記のもの以外にも種々のものを用いる
ことができろ。これらの結果を表１に示す。This effect does not only occur with ammonia;
The same phenomenon occurs with other basic gases such as hydrazine, methylamine, and diethylamine. Moreover, the effect is not temporary and does not recover for a long time. Further filter (1
For 4), various types can be used in addition to those listed in -1-. These results are shown in Table 1.
表 １ （リン酸アンチモンへの塩基性ガスの影響）＊
１ガ ス フィルター
フィルター なし各３００ｐｐｍ 部分酸化
硫酸銅 ４時間後 ２４時間後 ７２時間後活性
奏 担持活性炭 □ＮＨ！
１．０ １．０ ２．０ １．８
１．７ＮＨ７−ＮＨ３１，０１，０２，４
ＣＨ３−ＮＨ，１，０１，０２，８
＊１３００ｐｐｍのガスとの１時間の接触による抵抗値
の変化で、処理後の抵抗値と処理前の抵抗値との比を示
す、センサ温度１５０°Ｃ１水蒸気圧１０Ｔｏｒｒ、雰
囲気は空気。Table 1 (Effect of basic gas on antimony phosphate) *
1 gas filter
No filter 300ppm each Partial oxidation
Copper sulfate Active after 4 hours After 24 hours After 72 hours Supported activated carbon □NH!
1.0 1.0 2.0 1.8
1.7NH7-NH31,01,02,4 CH3-NH,1,01,02,8 *Change in resistance value due to contact with 1300ppm gas for 1 hour, resistance value after treatment and resistance value before treatment The sensor temperature is 150°C, the water vapor pressure is 10 Torr, and the atmosphere is air.
（ガスの検出装置）
第７図に、水素や一酸化炭素等の検出装置を示す。図に
おいて、（＋０２）はブ〔川・ン導電体を用いたガスセ
ンサで、（４）はアンチモン酸等のプロトン導電体、（
＋１２）はハウジング、（１１４）はエポキシ樹脂から
なる通気性の制限用ソールドである。ンールド（＋１４
）は水素等の拡散を抑制し電極（６）、（８）間にガス
濃度の差を設けるためのもので、ち密質、あるいは多孔
質を問うことなく通気性を制限し得るもので有れば、任
意のものを用いることができる。(Gas Detection Device) FIG. 7 shows a detection device for hydrogen, carbon monoxide, etc. In the figure, (+02) is a gas sensor using a conductor, (4) is a proton conductor such as antimonic acid, (
+12) is a housing, and (114) is a sole for restricting air permeability made of epoxy resin. N'rud (+14
) is for suppressing the diffusion of hydrogen, etc. and creating a difference in gas concentration between the electrodes (6) and (8), and can limit air permeability regardless of whether it is dense or porous. For example, any one can be used.
センサ（＋０２）の構造はこイ月こ限るものではなく、
他の公知のものや、導電体（４）に別の電極を接続し内
部起電力を測定するもの等も用いることが出来ろ。塩基
性ガスににろ高抵抗化の問題はセンサの構造によるもの
ではなく、プロトン導電体に一般的な問題である。The structure of the sensor (+02) is not limited to this.
Other known methods or methods that connect another electrode to the conductor (4) and measure the internal electromotive force may also be used. The problem of high resistance to basic gases is not due to the structure of the sensor, but is a general problem with proton conductors.
電極（６）、（８）には、短絡電流測定回路（＋１６）
や、起電力測定回路等を接続する。電極（６）、（８）
を低インピーダンスの負荷により短絡し、その間の電流
を測定すると、ガス濃度に比例する出力が得られる。ま
た電極（６）、（８）間の起電力を測定すると、ガス濃
度の対数に比例ケる出力が得られる。Short-circuit current measurement circuit (+16) is connected to electrodes (6) and (8).
or an electromotive force measurement circuit. Electrodes (6), (8)
If you short-circuit them with a low-impedance load and measure the current between them, you will get an output that is proportional to the gas concentration. Furthermore, when the electromotive force between the electrodes (6) and (8) is measured, an output proportional to the logarithm of the gas concentration can be obtained.
第８図に、アンチモン酸の短絡電流へのアンモニアの影
響を示１ｏ測定条件は２０℃・相対湿度７８％で、他の
点は第３図の場合と同等である。FIG. 8 shows the influence of ammonia on the short-circuit current of antimonic acid. The measurement conditions were 20° C. and 78% relative humidity, and the other points were the same as in FIG. 3.
アンモニアとの接触によりアンチモン酸の内部抵抗は増
太し、短絡電流は減少する。これに対Ｉ２て単味の活性
炭でもかなりの効果が得られるが、スルホン化活性炭を
用いるとアンモニアの影響を充分に除くことができる。Upon contact with ammonia, the internal resistance of antimonic acid increases and the short circuit current decreases. On the other hand, although a considerable effect can be obtained even with simple activated carbon in I2, the influence of ammonia can be sufficiently removed by using sulfonated activated carbon.
［発明の効果］
この発明では、アンモニア等の塩基性ガスによる劣化を
防止し、プロトン導電体を用いた雰囲気の検出装置の信
頼性を向」ニさせることができる。[Effects of the Invention] According to the present invention, deterioration caused by basic gases such as ammonia can be prevented, and the reliability of an atmosphere detection device using a proton conductor can be improved.
第１図は実施例の装置の一部断面図付き回路図、第２図
〜第６図は実施例の特性図、第７図は他の実施例の一部
断面図付き回路図、第８図はその特性図である。
（２）： プロトン導電体湿度センサ、（１０２）
プロトン導電体ガスセンサ、（４）： プロトン導電体
、
（１４）： 塩基性ガス吸収用フィルター。FIG. 1 is a circuit diagram with a partial sectional view of the device of the embodiment, FIGS. 2 to 6 are characteristic diagrams of the embodiment, FIG. 7 is a circuit diagram with a partial sectional diagram of another embodiment, and FIG. The figure shows its characteristic diagram. (2): Proton conductor humidity sensor, (102)
Proton conductor gas sensor, (4): Proton conductor, (14): Filter for basic gas absorption.
Claims (4)
出装置において、 塩基性ガス吸収剤を有効成分とするフィルターを設け、
塩基性ガスによるプロトン導電体の劣化を防止するよう
に構成したことを特徴とする、プロトン導電体雰囲気検
出装置。(1) In an atmosphere detection device using a proton conductor atmosphere sensor, a filter containing a basic gas absorbent as an active ingredient is installed,
A proton conductor atmosphere detection device, characterized in that the proton conductor is configured to prevent deterioration of the proton conductor due to basic gas.
気検出装置において、 前記塩基性ガス吸収剤は活性炭であることを特徴とする
、プロトン導電体雰囲気検出装置。(2) The proton conductor atmosphere detection device according to claim 1, wherein the basic gas absorbent is activated carbon.
気検出装置において、 前記塩基性ガス吸収剤は、部分酸化活性炭、スルホン化
活性炭、及び酸性物質を添加した活性炭、からなる群の
少なくとも一員の物質であることを特徴とするプロトン
導電体雰囲気検出装置。(3) In the proton conductor atmosphere detection device according to claim 1, the basic gas absorbent is at least a member of the group consisting of partially oxidized activated carbon, sulfonated activated carbon, and activated carbon added with an acidic substance. A proton conductor atmosphere detection device characterized by being a substance of
気検出装置において、 前記塩基性ガス吸収剤は、酸性物質を担持した多孔体で
あることを特徴とするプロトン導電体雰囲気検出装置。(4) The proton conductor atmosphere detection device according to claim 1, wherein the basic gas absorbent is a porous body supporting an acidic substance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61043743A JPH0640082B2 (en) | 1986-02-27 | 1986-02-27 | Proton conductor atmosphere detector |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61043743A JPH0640082B2 (en) | 1986-02-27 | 1986-02-27 | Proton conductor atmosphere detector |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62200257A true JPS62200257A (en) | 1987-09-03 |
| JPH0640082B2 JPH0640082B2 (en) | 1994-05-25 |
Family
ID=12672243
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61043743A Expired - Lifetime JPH0640082B2 (en) | 1986-02-27 | 1986-02-27 | Proton conductor atmosphere detector |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0640082B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006308502A (en) * | 2005-05-02 | 2006-11-09 | Mitsubishi Electric Corp | Device for detecting moisture density in sf6 gas |
| JP2011209184A (en) * | 2010-03-30 | 2011-10-20 | Gunze Ltd | Apparatus and method for detection of hydrogen gas |
-
1986
- 1986-02-27 JP JP61043743A patent/JPH0640082B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006308502A (en) * | 2005-05-02 | 2006-11-09 | Mitsubishi Electric Corp | Device for detecting moisture density in sf6 gas |
| JP4616069B2 (en) * | 2005-05-02 | 2011-01-19 | 三菱電機株式会社 | Device for detecting moisture concentration in SF6 gas |
| JP2011209184A (en) * | 2010-03-30 | 2011-10-20 | Gunze Ltd | Apparatus and method for detection of hydrogen gas |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0640082B2 (en) | 1994-05-25 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |