JPH0379802B2 - - Google Patents
Info
- Publication number
- JPH0379802B2 JPH0379802B2 JP56129971A JP12997181A JPH0379802B2 JP H0379802 B2 JPH0379802 B2 JP H0379802B2 JP 56129971 A JP56129971 A JP 56129971A JP 12997181 A JP12997181 A JP 12997181A JP H0379802 B2 JPH0379802 B2 JP H0379802B2
- Authority
- JP
- Japan
- Prior art keywords
- dielectric loss
- moisture
- humidity
- sensitive
- present
- 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
- 229910052573 porcelain Inorganic materials 0.000 claims description 6
- 229910020684 PbZr Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 description 12
- 239000010408 film Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 230000004044 response Effects 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- -1 Fe 2 O 3 Chemical class 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 229910002971 CaTiO3 Inorganic materials 0.000 description 2
- 229910003327 LiNbO3 Inorganic materials 0.000 description 2
- 229910012463 LiTaO3 Inorganic materials 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910002976 CaZrO3 Inorganic materials 0.000 description 1
- 229910017676 MgTiO3 Inorganic materials 0.000 description 1
- 229910020698 PbZrO3 Inorganic materials 0.000 description 1
- 229910002370 SrTiO3 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 229910021523 barium zirconate Inorganic materials 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002003 electrode paste Substances 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910014031 strontium zirconium oxide Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Landscapes
- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Inorganic Insulating Materials (AREA)
Description
本発明は、感湿誘電損失体素子に関するもので
ある。
感湿誘電損失体素子は湿度に敏感に感応し、湿
度によつてその誘電損失（誘電正接）が変化する
素子であり、湿度の測定用素子や、湿度調節用の
センサとして用いるものである。周知のように、
Fe2O3やAl2O3、Cr2O3、Ni2O3などの金属酸化物
は吸水性に優れており、そのため、このような性
質を利用して感湿抵抗体素子が作製されている。
ところが、上記金属酸化物を使用した感湿抵抗体
素子は、全般的に抵抗が高く、水分の吸脱着現象
により、抵抗変化があつても、これを電気的に精
度よく検出することが困難なものである。すなわ
ち、この種の素子は、たとえば、結露点の検出と
いつた高湿度領域での応用に限られている。
素子を測定の容易な抵抗値の素子とするために
これまで上記金属酸化物に、アルカリ金属系の物
質、たとえば、Na、Liなどの化合物を添加混合
することが試みられている。しかしながら、この
方法では、抵抗の絶対値が減少するものの、高湿
度の状態では、アルカリ金属系化合物が溶出し、
感湿抵抗特性が変化する。このような理由によ
り、実際にこれを使用することはむずかしい。ま
た、これらの素子は、物理吸着した水のイオン伝
導により、感湿特性を得ているものである。
たとえば、イオン化しやすい低濃度の成分を含
む雰囲気に触れるだけで感湿抵抗特性が変化す
る。
本発明は、かかる問題点を解決することができ
たもので、これまでの感湿抵抗体とは異なり、全
く新しい感湿誘電損失体素子を提供するものであ
る。
すなわち、本発明にかかる素子は、ABO3成分
（ただし、ABは、KTa、PbHf、LiTa、LiNb、
CaTi、PbZr、NaNb、KNb、PbTiのうちから
選ばれた１種）を主成分とする磁器もしくは膜に
少なくとも一対の電極を設けてなる素子であり、
湿度に応じて、電極間の誘電損失（誘電正接）が
大きく変化する現象を見出したものである。
本発明はこのような現象の発見に基づくもので
ある。また、組成を選ぶことにより、低湿度から
高湿度にかけて高い感度を示す素子を得ることが
できる。相対湿度−誘電正接特性は、低湿度から
高湿度までほぼ対数的に直線である。
さらに、詳細に述べるならば、本発明にかかる
組成物は一種の誘電体であり、その組成を選定す
ることによつて、湿度変化による誘電正接値の変
化の大きい素子を作ることができる。
しかも、本発明の素子は、ペロブスカイト形結
晶構造の化合物であり、その誘電正接の温度係数
も小さい。この素子に交流電圧を印加することに
より、電流と電圧の位相差を検出することによ
り、容易に相対湿度０〜100％の全湿度領域にお
いて湿度を検知することができる。さらにまた、
その湿度応答性も早いものである。
本発明にかかる組成物は、通常の磁器製造技術
は薄膜製造技術で簡単に製造することができるも
のである。
さらに、これは、いわゆる金属酸化物であり、
長期間大気中に放置しておいても、その表面状態
が変化しない。
本発明において、組成を前述のように特定した
理由は、ペロブスカイト形結晶構造の化合物であ
り、湿度変化に応じて誘電正接の変化が一義的に
決まるからである。そして、この素子は、低湿度
領域から高湿度領域にわたり高い感度を得ること
ができる。
以下本発明にかかる感湿誘電損失体素子の実施
例について、図面を用いて詳細に説明する。
第１図に本発明にかかる感湿誘電損失体素子の
実施例の代表的な構造を示す。第１図Ａは、バル
ク型の素子であり、第１図Ｂは膜型の素子であ
る。これら素子は、磁器であつても、あるいは膜
であつても、本質的な機能は同じである。図Ａに
おいて、１は磁器からなる感湿誘電損失体、２，
３は電極、４，５はリード線である。図Ｂにおい
て、６は膜状の感湿誘電損失体、７はその支持基
板、８，９はくし型電極、１０，１１はリード線
である。
まず、ABO3で示される感湿誘電損失体素子に
ついて述べる。
出発業料として、PbO、TiO2を湿式混合した
後、乾燥粉末とする。つぎに、この粉末原料を４
mm×４mm×0.25mmに成形（成形圧750Kg／cm2）し、
空気中において1150℃で２時間焼成してPbTiO3
の磁器からなる感湿誘電損失体１を作成した。さ
らに感湿誘電損失体にRuO2系電極ペーストを塗
布して温度800℃で焼付て一対の電極を形成した。
なお、電極はPt系、Ag系、Au系でも良好であ
る。また、ABO3で示される他の組成KTaO3、
PbHfO3、LiTaO3、LiNbO3、CaTiO3、
PbZrO3、NaNbO3、KNbO3についても同様な方
法にて感湿誘電損失体磁器を作成し、そして作製
された磁器に一対の電極を設け、感湿誘電損失体
とする。
そして前記によつて得た感湿誘電損失体の電極
の部分に白金リード線をRuO2系ペーストを用い
て800℃で焼付けて感湿誘電損失体素子とした。
また、感湿誘電損失体素子が膜タイプの場合、
スパツタリング法、蒸着法、スクリーン印刷法な
どにより、感湿誘電損失体の膜を形成して同様に
各種組成の素子を得ることができる。
第２図はPbTiO3系感湿誘電損失体素子の相対
湿度−誘電損失（誘電正接、ただし相対湿度０％
との比で表わす）の感度特性を示す。他の組成の
素子についての特性を下表に示す。
The present invention relates to a moisture-sensitive dielectric loss body element. A moisture-sensitive dielectric loss element is an element that is sensitive to humidity and whose dielectric loss (dielectric loss tangent) changes depending on the humidity, and is used as a humidity measurement element or a humidity adjustment sensor. As is well known,
Metal oxides such as Fe 2 O 3 , Al 2 O 3 , Cr 2 O 3 , and Ni 2 O 3 have excellent water absorption properties, so moisture-sensitive resistor elements are fabricated using these properties. ing.
However, moisture-sensitive resistor elements using the above-mentioned metal oxides generally have high resistance, and even if there is a change in resistance due to moisture adsorption/desorption, it is difficult to accurately detect this electrically. It is something. That is, this type of device is limited to applications in high humidity regions, such as detection of dew point, for example. In order to make an element with a resistance value that is easy to measure, attempts have been made to add and mix alkali metal-based substances, such as compounds such as Na and Li, to the metal oxide. However, although this method reduces the absolute value of resistance, under high humidity conditions, alkali metal compounds elute and
Moisture sensitive resistance characteristics change. For these reasons, it is difficult to actually use it. Furthermore, these elements obtain moisture-sensitive characteristics through ionic conduction of physically adsorbed water. For example, the moisture-sensitive resistance characteristics change simply by exposure to an atmosphere containing low-concentration components that are easily ionized. The present invention has been able to solve these problems, and provides a completely new moisture-sensitive dielectric loss element, unlike conventional moisture-sensitive resistors. That is, the device according to the present invention has three ABO components (where AB is KTa, PbHf, LiTa, LiNb,
An element in which at least one pair of electrodes is provided on a porcelain or film whose main component is one selected from CaTi, PbZr, NaNb, KNb, and PbTi,
We have discovered a phenomenon in which the dielectric loss (dielectric loss tangent) between electrodes changes significantly depending on the humidity. The present invention is based on the discovery of such a phenomenon. Furthermore, by selecting the composition, it is possible to obtain an element that exhibits high sensitivity from low humidity to high humidity. The relative humidity-dissipation tangent characteristic is approximately logarithmically linear from low humidity to high humidity. More specifically, the composition according to the present invention is a type of dielectric material, and by selecting its composition, an element whose dielectric loss tangent value changes greatly due to changes in humidity can be manufactured. Furthermore, the element of the present invention is a compound having a perovskite crystal structure, and its temperature coefficient of dielectric loss tangent is also small. By applying an alternating current voltage to this element and detecting the phase difference between current and voltage, humidity can be easily detected in the entire humidity range of 0 to 100% relative humidity. Furthermore,
Its humidity response is also fast. The composition according to the present invention can be easily manufactured using a thin film manufacturing technique, which is a conventional porcelain manufacturing technique. Furthermore, this is a so-called metal oxide,
Even if it is left in the atmosphere for a long time, its surface condition does not change. In the present invention, the reason why the composition is specified as described above is that it is a compound with a perovskite crystal structure, and the change in dielectric loss tangent is uniquely determined according to changes in humidity. Furthermore, this element can obtain high sensitivity from a low humidity region to a high humidity region. Embodiments of the moisture-sensitive dielectric loss body element according to the present invention will be described in detail below with reference to the drawings. FIG. 1 shows a typical structure of an embodiment of a moisture-sensitive dielectric loss body element according to the present invention. 1A shows a bulk type device, and FIG. 1B shows a film type device. These elements have the same essential function whether they are made of porcelain or film. In Figure A, 1 is a moisture-sensitive dielectric loss body made of porcelain, 2,
3 is an electrode, and 4 and 5 are lead wires. In FIG. B, 6 is a film-like moisture-sensitive dielectric loss body, 7 is its supporting substrate, 8 and 9 are comb-shaped electrodes, and 10 and 11 are lead wires. First, the moisture-sensitive dielectric loss body element denoted by ABO 3 will be described. As starting materials, PbO and TiO 2 are wet mixed and then made into a dry powder. Next, add this powder raw material to 4
Molded into mm×4mm×0.25mm (molding pressure 750Kg/cm 2 ),
PbTiO 3 was baked in air at 1150℃ for 2 hours.
A moisture-sensitive dielectric loss body 1 made of porcelain was prepared. Furthermore, RuO 2 -based electrode paste was applied to the moisture-sensitive dielectric loss body and baked at a temperature of 800°C to form a pair of electrodes.
Note that Pt-based, Ag-based, and Au-based electrodes are also suitable. Also, other compositions KTaO 3 denoted by ABO 3 ,
PbHfO3 , LiTaO3 , LiNbO3 , CaTiO3 ,
PbZrO 3 , NaNbO 3 , and KNbO 3 are used to produce moisture-sensitive dielectric loss ceramics in a similar manner, and a pair of electrodes is provided on the produced ceramics to form moisture-sensitive dielectric loss bodies. Then, a platinum lead wire was baked at 800° C. using RuO 2 paste on the electrode portion of the moisture-sensitive dielectric loss body obtained as described above to obtain a moisture-sensitive dielectric loss body element. In addition, if the moisture-sensitive dielectric loss element is a film type,
By forming a film of a moisture-sensitive dielectric loss material by a sputtering method, a vapor deposition method, a screen printing method, or the like, devices having various compositions can be similarly obtained. Figure 2 shows the relative humidity vs. dielectric loss (dielectric loss tangent, relative humidity 0%) of a PbTiO 3 moisture-sensitive dielectric loss element.
(expressed as a ratio of The characteristics for devices with other compositions are shown in the table below.
【表】【table】
【表】
第２図および上表より、本発明の素子は、前述
した各組成を主成分として構成するペロブスカイ
ト型構造のものが、湿度変化に対応して大きく誘
電正接が変化することが実験により判明した。ま
た前記組成を２種および３種組合せた素子につい
ても、実験した結果、湿度変化に対応して誘電正
接が変化し、感湿感度は、前記同様に得られた。
さらに、上記組成を少なくとも１種を含む主成
分からなる感湿誘電損失体素子を相対湿度40〜60
％から結露（相対湿度100％）の湿度サイクルを
105回繰返して試験した。その結果、湿度−誘電
正接特性の変化量は数％以内であり、きわめて安
定なものであることを確認した。また、湿度応答
性については、相対湿度０〜100％において、応
答速度は、数秒以内であり、きわめて早い。
本発明の素子は、従来の感湿抵抗特性に示すイ
オン伝導タイプとは異なり、素子に吸着した水分
そのものによる誘電損失すなわち誘電分散によつ
て生じる誘電正接の変化であるため、きわめて安
定で、しかも、各種有機ガスや酸性ガスなどに対
し、安定した湿度検知が知られるものである。
さらに、本発明において、各種添加物として、
BaTiO3、SrTiO3、MgTiO3、CaTiO3、
KTaO3、PbHfO3、LiTaO3、LiNbO3、
BaZrO3、CaZrO3、SrZrO3、MgZrO3、PbZrO3、
NaNbO3、KNbO3、PbTiO3、MgCr2O4などを
１種または複数種（ただし主成分と同種は除く）
加えると、応答性がよく、特性劣化のきわめて少
ない高感度の感湿誘電損失体素子を得ることがで
きる。
以上に説明したように、本発明にかかる感湿誘
電損失体素子は、湿度−誘電正接特性を有する全
く新しい感湿素子であり、高安定性と高精度検知
を行うことができ、産業界にとつて価値大なる感
湿誘電損失体素子を提供する。[Table] From Figure 2 and the table above, experiments have shown that the element of the present invention has a perovskite structure mainly composed of the above-mentioned compositions, and that the dielectric loss tangent changes greatly in response to changes in humidity. found. Further, as a result of experiments for elements in which two or three of the above compositions were combined, the dielectric loss tangent changed in response to changes in humidity, and the same humidity sensitivity was obtained as described above. Furthermore, a moisture-sensitive dielectric loss body element consisting of a main component containing at least one of the above compositions is heated at a relative humidity of 40 to 60%.
Humidity cycle from % to condensation (100% relative humidity)
The test was repeated 10 times. As a result, it was confirmed that the amount of change in the humidity-dielectric loss tangent characteristic was within several percent, and that it was extremely stable. Furthermore, regarding the humidity response, the response speed is within a few seconds at relative humidity of 0 to 100%, which is extremely fast. The element of the present invention differs from the conventional ion-conducting type shown in the moisture-sensitive resistance characteristics, and is extremely stable because the change in dielectric loss tangent occurs due to dielectric loss due to the moisture itself adsorbed on the element, that is, dielectric dispersion. It is known that stable humidity detection is possible for various organic gases, acidic gases, etc. Furthermore, in the present invention, as various additives,
BaTiO3 , SrTiO3 , MgTiO3 , CaTiO3 ,
KTaO3 , PbHfO3 , LiTaO3 , LiNbO3 ,
BaZrO3 , CaZrO3 , SrZrO3 , MgZrO3 , PbZrO3 ,
One or more types of NaNbO 3 , KNbO 3 , PbTiO 3 , MgCr 2 O 4 etc. (excluding the same type as the main component)
In addition, a highly sensitive moisture-sensitive dielectric loss element with good responsiveness and extremely little deterioration of characteristics can be obtained. As explained above, the moisture-sensitive dielectric loss element according to the present invention is a completely new moisture-sensitive element that has humidity-dielectric loss tangent characteristics, is capable of high stability and high-precision detection, and is widely used in industry. To provide a moisture-sensitive dielectric loss body element of great value.
第１図Ａ，Ｂはそれぞれ本発明にかかる素子の
実施例の代表的な構造を示す図、第２図はその湿
度−誘電正接特性の代表例を示す特性図である。
１，６……感湿誘電損失体、２，３，８，９…
…電極。
FIGS. 1A and 1B are diagrams each showing a typical structure of an embodiment of an element according to the present invention, and FIG. 2 is a characteristic diagram showing a typical example of its humidity-dielectric loss tangent characteristics. 1, 6...Moisture sensitive dielectric loss body, 2, 3, 8, 9...
…electrode.
Claims (1)
LiTa、LiNb、CaTi、PbZr、NaNb、KNb、
PbTiのうちから選ばれた１種）を主成分とする
磁器または膜を有する感湿誘電損失体素子。1 ABO 3 components (AB is KTa, PbHf,
LiTa, LiNb, CaTi, PbZr, NaNb, KNb,
A moisture-sensitive dielectric loss material element having a porcelain or film whose main component is PbTi (one type selected from PbTi).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56129971A JPS5832303A (en) | 1981-08-19 | 1981-08-19 | Humidity sensitive dielectric loss element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56129971A JPS5832303A (en) | 1981-08-19 | 1981-08-19 | Humidity sensitive dielectric loss element |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3020812A Division JPH04212049A (en) | 1991-02-14 | 1991-02-14 | Moisture-responsive dielectric loss body element |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5832303A JPS5832303A (en) | 1983-02-25 |
| JPH0379802B2 true JPH0379802B2 (en) | 1991-12-20 |
Family
ID=15022956
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56129971A Granted JPS5832303A (en) | 1981-08-19 | 1981-08-19 | Humidity sensitive dielectric loss element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5832303A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62138360A (en) * | 1985-12-10 | 1987-06-22 | 三菱鉱業セメント株式会社 | Dielectric ceramic composition |
-
1981
- 1981-08-19 JP JP56129971A patent/JPS5832303A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5832303A (en) | 1983-02-25 |
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