JPH076941B2 - PH sensor - Google Patents
PH sensorInfo
- Publication number
- JPH076941B2 JPH076941B2 JP1003285A JP328589A JPH076941B2 JP H076941 B2 JPH076941 B2 JP H076941B2 JP 1003285 A JP1003285 A JP 1003285A JP 328589 A JP328589 A JP 328589A JP H076941 B2 JPH076941 B2 JP H076941B2
- Authority
- JP
- Japan
- Prior art keywords
- conductive layer
- solid electrolyte
- ion conductive
- sensor
- layer
- 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.)
- Expired - Lifetime
Links
Landscapes
- Measuring Oxygen Concentration In Cells (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、濃淡電池作用を利用したPHセンサーに関する
ものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial field of use] The present invention relates to a PH sensor utilizing a concentration cell action.
従来のこの種PHセンサーとしては、金属導体及びその素
地金属の酸化物膜で形成される電荷移動層上に、イット
リア安定化ジルコニア（以下「YSZ」という）からなる
イオン導電層を密着形成して、イオン導電層の両面間に
生じた電位差によりPHを測定しうるように構成したもの
が知られている。As a conventional PH sensor of this type, an ion conductive layer made of yttria-stabilized zirconia (hereinafter referred to as "YSZ") is formed by adhesion on a charge transfer layer formed of a metal conductor and an oxide film of the base metal. It is known that PH can be measured by a potential difference generated between both surfaces of the ion conductive layer.
しかしながら、かかる従来センサーは、低音域では極め
て精度が悪く、特に室温付近の温度域では到底使用でき
ないものである。このため、500℃以上の高温域でしか
実用されておらず、広範な温度域での使用が不可能なも
のである。これは、第４図に示す如く、YSZのイオン導
電率が500℃までの低温領域では極めて低く、したがっ
てイオン拡散速度が極めて遅くなるためであると考えら
れる。However, such a conventional sensor is extremely inaccurate in the low sound range and cannot be used at all in the temperature range near room temperature. For this reason, it is used only in a high temperature range of 500 ° C or higher, and cannot be used in a wide temperature range. It is considered that this is because, as shown in FIG. 4, the ionic conductivity of YSZ is extremely low in the low temperature region up to 500 ° C., and therefore the ion diffusion rate becomes extremely slow.
また、応答速度を向上させるためにはYSZ層を薄膜化す
ることが望ましいが、このようにすると、金属導体との
線膨張率差によるYSZ層が剥離し易くなり、耐久性が大
幅に低下する。したがって、YSZ層はこれを薄膜化でき
ず、どうしても応答性に劣るといった問題がある。Further, in order to improve the response speed, it is desirable to thin the YSZ layer, but this makes it easier to peel off the YSZ layer due to the difference in the linear expansion coefficient with the metal conductor, and the durability is greatly reduced. . Therefore, the YSZ layer cannot be thinned, and there is a problem that the response is inevitably poor.
本発明は、このような従来センサーにおける問題を解決
して、室温付近の低温から500℃以上の高温に至る広範
な温度域において好適に使用でき、且つ応答性及び耐久
性に優れたPHセンサーを提供することを目的とするもの
である。The present invention solves the above problems in conventional sensors, and is suitable for use in a wide temperature range from a low temperature near room temperature to a high temperature of 500 ° C. or higher, and a PH sensor having excellent responsiveness and durability. It is intended to be provided.
この課題を解決した本発明のPHセンサーは、金属導体及
びその素地金属の酸化物膜で形成される電荷移動層上
に、異種の固体電解質膜を積層してなるイオン導電層を
密着形成してあり、各固体電解質膜がBi2O3を主成分と
してなるものである。The PH sensor of the present invention which has solved this problem, the charge transfer layer formed by the oxide film of the metal conductor and its base metal, the ion conductive layer formed by laminating different kinds of solid electrolyte membrane is formed in close contact. Yes, each solid electrolyte membrane contains Bi 2 O 3 as a main component.
具体的には、各固体電解質膜は、Bi2O3にSb2O3,CeO2,Te
O2,Ta2O5,Nb2O5,WO3,MnO2等の酸化物セラミックを一種
若しくは二種以上固溶させた固体電解質材で構成され
る。酸化物セラミックの固溶量は２〜10mol％としてお
くことが好ましい。イオン導電層は、CVD,スパッタリン
グ，イオンプレーティング等によって形成されるが、そ
の層厚さは0.01〜50μｍとしておくことが好ましい。イ
オン導電層を構成する固体電解質膜の積層数は、PH測定
条件等に応じて適宜に設定される。Specifically, each solid electrolyte membrane consists of Bi 2 O 3 , Sb 2 O 3 , CeO 2 , and Te.
It is composed of a solid electrolyte material in which one or more kinds of oxide ceramics such as O 2 , Ta 2 O 5 , Nb 2 O 5 , WO 3 and MnO 2 are solid-solved. The solid solution amount of the oxide ceramic is preferably 2 to 10 mol%. The ion conductive layer is formed by CVD, sputtering, ion plating or the like, and the layer thickness is preferably 0.01 to 50 μm. The number of stacked solid electrolyte membranes constituting the ion conductive layer is appropriately set according to the PH measurement conditions and the like.
Bi2O3を主成分としてなる固体電解質材、例えばSb2O3−
Bi2O3では、第３図に示す如く、室温から800℃に至る広
範な温度域で高いイオン導電率を有する。すなわち、室
温付近におけるイオン導電率でも、500〜600℃における
YSZのイオン導電率と略同一となっている。かかる特性
は、Bi2O3にSb2O3以外の前記酸化セラミックを固溶させ
た場合においても同様である。したがって、イオン導電
層をBi2O3を主成分としてなるもので構成することによ
って、500℃以上の高温域においては勿論、500℃以下の
低温域、特に室温程度の低温域においても、PHを精度良
く検出しうる。A solid electrolyte material containing Bi 2 O 3 as a main component, for example, Sb 2 O 3 −
Bi 2 O 3 has a high ionic conductivity in a wide temperature range from room temperature to 800 ° C., as shown in FIG. That is, even at ionic conductivity near room temperature,
It is almost the same as the ionic conductivity of YSZ. Such characteristics are the same when the oxide ceramics other than Sb 2 O 3 are dissolved in Bi 2 O 3 as a solid solution. Therefore, by configuring the ion conductive layer with Bi 2 O 3 as a main component, the PH can be maintained not only in a high temperature range of 500 ° C. or higher, but also in a low temperature range of 500 ° C. or lower, particularly at a low temperature of about room temperature. It can be detected accurately.
また、イオン導電層を異種の固体電解質膜で積層形成し
たから、熱膨張率勾配が生じてイオン導電層が素地金属
に充分になじむことになる。したがって、イオン導電層
の薄膜化及び剥離防止を共に図ることができ、応答性及
び耐久性を向上させうる。Further, since the ionic conductive layer is formed by laminating different kinds of solid electrolyte membranes, a thermal expansion coefficient gradient is generated and the ionic conductive layer is sufficiently adapted to the base metal. Therefore, it is possible to reduce the thickness of the ion conductive layer and prevent peeling of the ion conductive layer, and improve responsiveness and durability.
しかも、異種酸化物膜間で非化学量論的な多元酸化物、
つまり酸素欠陥の多い酸化物が生成されることから、イ
オン導電率の更なる向上が期待される。Moreover, non-stoichiometric multi-component oxides between different oxide films,
That is, since oxides with many oxygen defects are generated, further improvement in ionic conductivity is expected.
以下、本発明の実施例を第１図及び第２図について説明
する。An embodiment of the present invention will be described below with reference to FIGS. 1 and 2.
この実施例のPHセンサーあっては、第１図に示す如く、
銅線からなる基盤電極１の一端部分表面に、CVD,スパッ
タリング，イオンプレーティング等によって、イオン導
電層２が被覆形成されている。イオン導電層２の表面に
は、図示していないが、公知のものと同様にPt等からな
る測定側電極が接着されている。In the PH sensor of this embodiment, as shown in FIG.
An ion conductive layer 2 is formed on the surface of one end of the base electrode 1 made of a copper wire by CVD, sputtering, ion plating or the like. Although not shown, a measurement-side electrode made of Pt or the like is adhered to the surface of the ionic conductive layer 2, like a known one.
イオン導電層２は、第２図に示す如く、２種の固体電解
質膜2a,2bを積層してなる。積層厚さは、0.01〜50μｍ
とされている。一方の固体電解質膜2aはSb2O3−Bi2O3か
らなり、他方の固体電解質膜2bはWO3−Bi2O3からなる。
Bi2O3に対するSb2O3及びWO3の固溶量は、夫々２〜10mol
％とされている。The ion conductive layer 2 is formed by laminating two kinds of solid electrolyte membranes 2a and 2b as shown in FIG. Layer thickness is 0.01-50 μm
It is said that. One of the solid electrolyte membrane 2a is composed Sb 2 O 3 -Bi 2 O 3 , other solid electrolyte film 2b is made of WO 3 -Bi 2 O 3.
The solid solution amounts of Sb 2 O 3 and WO 3 with respect to Bi 2 O 3 are 2 to 10 mol, respectively.
It is said to be%.
基盤電極１とイオン導電層２との間には、電極素地金属
の酸化物Cu2Oによる酸化物膜1aが形成されており、この
酸化物膜1aと電極１の素地層とで電荷移動層１′が形成
されている。An oxide film 1a made of an oxide Cu 2 O of an electrode base metal is formed between the base electrode 1 and the ion conductive layer 2. The oxide film 1a and the base layer of the electrode 1 form a charge transfer layer. 1'is formed.
以上の説明から明らかなように、本発明によれば、Bi2O
3を主成分とする固体電解質膜を積層したから、イオン
導伝性が良好となると共に、高温状態と低温状態との繰
り返しにおけるイオン導伝性に関するヒステリスシスを
小さくし得て、両状態の繰り返しにおける耐久性，応答
性を高めることができる。したがって室温から500℃以
上の高温に至る広範囲の温度域においてPHを精度良く検
出することができ、しかも応答性及び耐久性に優れたPH
センサーを提供することができる。As is clear from the above description, according to the present invention, Bi 2 O
Since the solid electrolyte membrane containing 3 as a main component is laminated, the ion conductivity becomes good, and the hysteresis related to the ion conductivity in the high temperature state and the low temperature state can be reduced, and in the repetition of both states. It is possible to improve durability and responsiveness. Therefore, PH can be accurately detected in a wide temperature range from room temperature to a high temperature of 500 ° C or higher, and the PH has excellent responsiveness and durability.
A sensor can be provided.
第１図は本発明に係るPHセンサーの一実施例を示す要部
の断面図、第２図はその一部の拡大図、第３図はSb2O3
−Bi2O3におけるイオン導電率と温度との関係を示す特
性曲線図であり、第４図はYSZにおけるイオン導電率と
温度との関係を示す特性曲線図である。 １……電極基盤（金属導体）、１′……電荷移動層、1a
……酸化物膜、２……イオン導電層、2a,2b……固体電
解質膜。FIG. 1 is a sectional view of an essential part showing an embodiment of a PH sensor according to the present invention, FIG. 2 is an enlarged view of a part thereof, and FIG. 3 is Sb 2 O 3
FIG. 4 is a characteristic curve diagram showing the relationship between ionic conductivity and temperature in —Bi 2 O 3 , and FIG. 4 is a characteristic curve diagram showing the relationship between ionic conductivity and temperature in YSZ. 1 ... Electrode substrate (metal conductor), 1 '... Charge transfer layer, 1a
...... Oxide film, 2 ・ ・ ・ Ion conductive layer, 2a, 2b …… Solid electrolyte film.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭59−154351（ＪＰ，Ａ) 特開 昭56−77751（ＪＰ，Ａ) 特開 昭58−15067（ＪＰ，Ａ) 特開 昭56−40750（ＪＰ，Ａ) 特開 昭54−99693（ＪＰ，Ａ) 特開 昭59−227727（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-59-154351 (JP, A) JP-A-56-77751 (JP, A) JP-A-58-15067 (JP, A) JP-A-56- 40750 (JP, A) JP 54-99693 (JP, A) JP 59-227727 (JP, A)
Claims (1)
成される電荷移動層上に、異種の固体電解質膜を積層し
てなるイオン導電層を密着形成してあり、各固体電解質
膜がBi2O3を主成分としてなることを特徴とするPHセン
サー。1. An ion conductive layer formed by laminating different kinds of solid electrolyte membranes is closely formed on a charge transfer layer formed of a metal conductor and an oxide film of a base metal thereof, and each solid electrolyte membrane is PH sensor characterized by containing Bi 2 O 3 as a main component.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1003285A JPH076941B2 (en) | 1989-01-10 | 1989-01-10 | PH sensor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1003285A JPH076941B2 (en) | 1989-01-10 | 1989-01-10 | PH sensor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02183151A JPH02183151A (en) | 1990-07-17 |
| JPH076941B2 true JPH076941B2 (en) | 1995-01-30 |
Family
ID=11553132
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1003285A Expired - Lifetime JPH076941B2 (en) | 1989-01-10 | 1989-01-10 | PH sensor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH076941B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114280125B (en) * | 2021-11-17 | 2022-09-16 | 广东省科学院测试分析研究所(中国广州分析测试中心) | Photoelectrochemistry flexible wearable sweat pH sensor based on bismuth oxide p-n type transition potential |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2757985B2 (en) * | 1977-12-24 | 1979-11-22 | Max-Planck-Institut Fuer Eisenforschung Gmbh, 4000 Duesseldorf | Method for producing an electrochemical immersion probe measuring cell for determining the activity of elements dissolved in molten metal, in particular oxygen |
| JPS5640750A (en) * | 1979-09-11 | 1981-04-17 | Yamazato Erekutoronaito Kk | Measuring element of oxygen concentration |
| US4264424A (en) * | 1979-10-12 | 1981-04-28 | General Electric Company | Hydrogen ion sensor having a membrane sheath of an oxygen ion conducting ceramic |
| JPS5815067A (en) * | 1981-07-13 | 1983-01-28 | セントラル硝子株式会社 | Bi2o3 composition of mainly delta phase at ordinary temperature, specific use, manufacture and manufacturing apparatus |
-
1989
- 1989-01-10 JP JP1003285A patent/JPH076941B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02183151A (en) | 1990-07-17 |
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