JPS6355845B2 - - Google Patents
Info
- Publication number
- JPS6355845B2 JPS6355845B2 JP57095226A JP9522682A JPS6355845B2 JP S6355845 B2 JPS6355845 B2 JP S6355845B2 JP 57095226 A JP57095226 A JP 57095226A JP 9522682 A JP9522682 A JP 9522682A JP S6355845 B2 JPS6355845 B2 JP S6355845B2
- Authority
- JP
- Japan
- Prior art keywords
- humidity
- moisture
- change
- humidity sensor
- resistance
- 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
Links
- 229910011250 Li3Zr2Si2PO12 Inorganic materials 0.000 claims description 15
- 239000000919 ceramic Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 3
- 239000000463 material Substances 0.000 description 12
- 229910010293 ceramic material Inorganic materials 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 229910052688 Gadolinium Inorganic materials 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910013553 LiNO Inorganic materials 0.000 description 1
- 229910003249 Na3Zr2Si2PO12 Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Description
【発明の詳細な説明】
本発明は、セラミツク感湿体を用いた斜度セン
サに関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an inclination sensor using a ceramic moisture sensitive body.
従来の湿度センサは、有機材料、セラミツク材
料を感湿体として用いているものが大部分を占め
ている。湿度測定には感湿体への水分の吸着によ
る電気抵抗の変化を応用しているものがほとんど
である。湿度センサでは水分の吸脱着が容易であ
ることが必要であり、加熱クリーニングにより吸
着前の表面状態に戻すことができることが必要で
ある。感湿体として有機材料を用いた場合には、
耐熱性に劣るため加熱クリーニングができないと
いう欠点がある。 Most conventional humidity sensors use organic materials or ceramic materials as moisture sensing elements. Most humidity measurements apply changes in electrical resistance due to adsorption of moisture to a humidity sensitive element. Humidity sensors need to be able to easily absorb and desorb moisture, and need to be able to restore the surface state before adsorption by heating and cleaning. When an organic material is used as a moisture sensitive body,
It has the disadvantage that it cannot be heated and cleaned because of its poor heat resistance.
セラミツク材料を感湿体として用いる場合も同
様に水分の吸脱着が容易であることが必要であ
る。金属酸化物系セラミツク材料の場合でも高温
加熱クリーニングにより表面構造が変化するもの
が多く、繰り返し使用することができないものが
多い。又、従来知られているセラミツク感湿体で
は、湿度の変化による導電率の変化が湿度０％〜
100％で大体104のオーダーである。しかしなが
ら、感度を上げるためには導電率の変化が更に大
きいことが必要である。したがつて従来から導電
率の変化が上記より更に大きい材料の出現が望ま
れていた。 When using a ceramic material as a moisture sensitive material, it is also necessary that it can easily absorb and desorb moisture. Even in the case of metal oxide-based ceramic materials, the surface structure of many materials changes due to high-temperature heating cleaning, and many materials cannot be used repeatedly. In addition, in the conventionally known ceramic moisture-sensitive body, the change in conductivity due to changes in humidity varies from 0% humidity to
100% is approximately on the order of 10 4 . However, increasing the sensitivity requires a larger change in conductivity. Therefore, it has been desired for a long time that a material exhibiting a larger change in electrical conductivity than the above-mentioned one has been developed.
本発明は、多孔質構造を有しており、吸湿性の
良いLi3Zr2Si2PO12、及びそのZrをMg、Zn等の
２価元素、希土類元素及びSc等の三価元素、及
びTiの４価元素で置換した材料を感湿体として
用いたことを特徴とするもので、その目的は、感
度が高く、しかも長期間の繰り返し使用に耐え得
る湿度センサを提供することにある。 The present invention uses Li 3 Zr 2 Si 2 PO 12 which has a porous structure and has good hygroscopicity, and its Zr is mixed with divalent elements such as Mg and Zn, trivalent elements such as rare earth elements and Sc, and It is characterized by using a material substituted with a tetravalent element of Ti as a humidity sensor, and its purpose is to provide a humidity sensor that has high sensitivity and can withstand repeated use over a long period of time.
以下、本発明について詳細に説明する。 The present invention will be explained in detail below.
湿度センサ用として使用される感湿体として
は、電気抵抗の湿度依存性が大きく、水分の吸脱
着性が良いことが必要である。Li3Zr2Si2PO12は、
本来Liイオン導電性の固体電解質であり、結晶構
造も三次元的網目構造をしており、多孔質構造を
示す。そのため、この系の材料は吸湿性が著し
く、また100〜150℃程度の加熱処理により水分の
脱離が容易であり、その繰り返しにより結晶が破
壊することも表面構造が変化することもない。 A moisture sensitive body used as a humidity sensor needs to have a high dependence of electrical resistance on humidity and good moisture adsorption/desorption properties. Li 3 Zr 2 Si 2 PO 12 is
It is originally a solid electrolyte that conducts Li ions, and its crystal structure has a three-dimensional network structure and exhibits a porous structure. Therefore, this type of material has remarkable hygroscopicity, and moisture is easily removed by heat treatment at about 100 to 150°C, and repeating this process does not destroy the crystals or change the surface structure.
Li3Zr2Si2PO12の導電率は、室温において湿度
０％で、〜６×10-11Ω-1cm-1であるが、湿度85
％で２×10-4Ω-1cm-1まで増大し、その変化量は
〜106のオーダーにまで達する。 The conductivity of Li 3 Zr 2 Si 2 PO 12 is ~6 × 10 -11 Ω -1 cm -1 at room temperature and 0% humidity, but at 85 Ω
% to 2×10 −4 Ω −1 cm −1 , and the amount of change reaches the order of ~10 6 .
Li3Zr2Si2PO12は、そのZrを２価、３価、４価
の元素で置換できる。Zn、Mg、希土類元素
（Sn、Gd、Dy、La等）Tiは、いずれもZrの5at
％まで置換し、固溶体を得ることができる。又
Scは25at％まで固溶する。 Zr in Li 3 Zr 2 Si 2 PO 12 can be replaced with divalent, trivalent, or tetravalent elements. Zn, Mg, rare earth elements (Sn, Gd, Dy, La, etc.) Ti are all 5at of Zr
% to obtain a solid solution. or
Sc dissolves up to 25at%.
Li3Zr2Si2PO12のZrを上記のように置換した材
料の乾燥した状態、湿度０％での導電率は、
Li3Zr2Si2PO12の導電率の1/10〜3/10である。又、
高湿度での導電率はほとんど同じであるから、湿
度変化による導電率の変化量は、Zrの数at％の置
換により増加する。 The conductivity of the material in which Zr in Li 3 Zr 2 Si 2 PO 12 is replaced as above in the dry state at 0% humidity is:
The conductivity is 1/10 to 3/10 that of Li 3 Zr 2 Si 2 PO 12 . or,
Since the electrical conductivity at high humidity is almost the same, the amount of change in electrical conductivity due to humidity changes increases by substituting several at% of Zr.
次に、本発明を実施例に沿つて説明するが、本
発明は、これらによりなんら限定されるものでは
ない。 Next, the present invention will be explained with reference to Examples, but the present invention is not limited to these in any way.
実施例 １
感湿体としてLi3Zr2Si2PO12を用いた場合につ
いて述べる。素子構造を第１図に示す。感湿体Ａ
の両面に銀電極１を形成し、これに測定用のリー
ド端子２を付けたものが基本構造である。電極
は、銀のみならず、Au、Pt、Al、Pd、Ag−Pd
等を使用することも可能である。この素子に微小
電流（10〜100μAを流してその電圧変化を測定す
るか、直接抵抗変化を測定することによつて湿度
を測定することができる。Example 1 A case will be described in which Li 3 Zr 2 Si 2 PO 12 is used as the moisture sensitive material. The device structure is shown in FIG. Humidity sensitive body A
The basic structure is that silver electrodes 1 are formed on both sides of the electrode, and lead terminals 2 for measurement are attached to this. Electrodes include not only silver but also Au, Pt, Al, Pd, Ag-Pd
It is also possible to use . Humidity can be measured by passing a minute current (10 to 100 μA) through this element and measuring the voltage change, or by directly measuring the resistance change.
次に感湿体の作製について述べる。まず、出発
原料であるNa2CO3、ZrO2、NH4H2PO4を
Na3Zr2Si2PO12なる組成式になるように秤量し、
混合した後、1250℃で６時間大気中で焼成する。
これを粉砕し、重量比で10倍のLiNO3を加え、
白金るつぼ中にて、350℃で28時間熱処理を行い、
NaとLiのイオン置換を行つた。これを十分水洗
することにより過剰のLiNO3、及びNaNO3を除
去し乾燥する。得られたLi3Zr2Si2PO12粉末を540
℃で500Kg／cm2のプレス圧で２時間ホツトプレス
法により作製した。この材料を用いて、第１図に
示した素子を作製し、その抵抗を測定した。第２
図に抵抗の湿度依存性を示す。抵抗値は、湿度の
変化に対して指数関数的に変化する。例えば20℃
における場合、湿度０％のとき1.7×1010Ω、85
％のとき４×103で６桁の変化を示す。また、可
逆性の面も高湿度から低湿度側へ走査した場合の
抵抗のずれも小さく、100〜150℃で加熱処理をす
ることにより、容易に元に復帰する。 Next, the preparation of the humidity sensitive body will be described. First, the starting materials Na 2 CO 3 , ZrO 2 , NH 4 H 2 PO 4
Weigh it so that the composition formula is Na 3 Zr 2 Si 2 PO 12 ,
After mixing, it is baked in the air at 1250°C for 6 hours.
Grind this, add 10 times more LiNO3 by weight,
Heat treated at 350℃ for 28 hours in a platinum crucible.
Ion replacement of Na and Li was performed. This is thoroughly washed with water to remove excess LiNO 3 and NaNO 3 and dried. The obtained Li 3 Zr 2 Si 2 PO 12 powder was
It was produced by hot pressing at a temperature of 500 kg/cm 2 for 2 hours. Using this material, the element shown in FIG. 1 was manufactured and its resistance was measured. Second
The figure shows the humidity dependence of resistance. The resistance value changes exponentially with changes in humidity. For example 20℃
1.7×10 10 Ω at 0% humidity, 85
When it is %, it shows a change of 6 digits with 4×10 3 . In addition, the reversible surface also shows a small deviation in resistance when scanning from high humidity to low humidity, and can be easily restored to its original state by heat treatment at 100 to 150°C.
実施例 ２
Li3Zr2Si2PO12のZrをZn、Mg、Sm、Gd、Sc、
Tiで置換した、Li3Zr1.9Zn0.2Si2PO12、Li3Zr1.9
Mg0.2Si2PO12、Li3.05Zr1.9Sm0.1Si2PO12、Li3.05
Zr1.9Gd0.1Si2PO12、Li3.25Zr1.75Sc0.25Si2PO12及び
Li3Zr1.9Ti0.1Si2PO12を感湿体として用いた湿度セ
ンサーを作製した。構造は実施例１と同じであ
る。感湿体であるセラミツク材料の作製は、出発
原料の段階で添加元素を組成式に従い秤量、添加
し、後は実施例１と同様の方法で作製した。これ
らの材料を感湿体として用いたセンサの電気抵抗
の湿度依存性は、実施例１のLi3Zr2Si2PO12を用
いた場合とほとんど同様であるが、乾燥状態での
導電率が小さい分だけ電気抵抗の湿度に対する変
化量が大きい。Example 2 Zr of Li 3 Zr 2 Si 2 PO 12 was replaced with Zn, Mg, Sm, Gd, Sc,
Li 3 Zr 1.9 Zn 0.2 Si 2 PO 12 , Li 3 Zr 1.9 substituted with Ti
Mg 0.2 Si 2 PO 12 , Li 3.05 Zr 1.9 Sm 0.1 Si 2 PO 12 , Li 3.05
Zr 1.9 Gd 0.1 Si 2 PO 12 , Li 3.25 Zr 1.75 Sc 0.25 Si 2 PO 12 and
A humidity sensor using Li 3 Zr 1.9 Ti 0.1 Si 2 PO 12 as a humidity sensor was fabricated. The structure is the same as in Example 1. The ceramic material used as the moisture sensitive body was prepared by weighing and adding additional elements according to the composition formula at the stage of starting raw materials, and then using the same method as in Example 1. The humidity dependence of the electrical resistance of a sensor using these materials as a humidity sensitive body is almost the same as that of Example 1 using Li 3 Zr 2 Si 2 PO 12 , but the conductivity in a dry state is The smaller the value, the greater the amount of change in electrical resistance with respect to humidity.
以上説明したように、本発明による
Li3Zr2Si2PO12系材料を用いた湿度センサは、
Li3Zr2Si2PO12の吸湿性の良さ、吸着水分による
導電率の変化の大きさにより、湿度の変化に対し
て105Ωのオーダー以上の抵抗変化を示す。この
ように、この材料を感湿体として用いた湿度セン
サーは高感度が得られる。 As explained above, according to the present invention
Humidity sensors using Li 3 Zr 2 Si 2 PO 12 -based materials are
Due to the good hygroscopicity of Li 3 Zr 2 Si 2 PO 12 and the magnitude of the change in conductivity due to adsorbed moisture, it exhibits a resistance change on the order of 10 5 Ω or more in response to changes in humidity. In this way, a humidity sensor using this material as a humidity sensor can achieve high sensitivity.
第１図は本発明による湿度センサの断面図、第
２図はLi3Zr2Si2PO12を用いた素子の抵抗の湿度
依存性を示したグラフである。
Ａ……感湿体、１……電極、２……リード端
子。
FIG. 1 is a cross-sectional view of a humidity sensor according to the present invention, and FIG. 2 is a graph showing the humidity dependence of the resistance of an element using Li 3 Zr 2 Si 2 PO 12 . A...Moisture sensitive body, 1...electrode, 2...lead terminal.
Claims (1)
て用いることを特徴とする湿度センサ。 ２ Li3Zr2Si2PO12のZrを０〜5at％の範囲でMg，
Zn、希土類元素、及びTi等の２価、３価、４価
の元素、あるいは、０〜25at％の範囲でScのい
ずれかあるいは複数個の置換により得られる磁器
組成物を感湿体として用いることを特徴とする湿
度センサ。[Claims] A humidity sensor characterized in that a ceramic composition of 1 Li 3 Zr 2 Si 2 PO 12 is used as a humidity sensor. 2 Li 3 Zr 2 Si 2 PO 12 Zr is added with Mg in the range of 0 to 5 at%,
A ceramic composition obtained by substituting one or more of divalent, trivalent, and tetravalent elements such as Zn, rare earth elements, and Ti, or Sc in the range of 0 to 25 at% is used as a moisture sensitive body. A humidity sensor characterized by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57095226A JPS58212101A (en) | 1982-06-03 | 1982-06-03 | Moisture sensor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57095226A JPS58212101A (en) | 1982-06-03 | 1982-06-03 | Moisture sensor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58212101A JPS58212101A (en) | 1983-12-09 |
| JPS6355845B2 true JPS6355845B2 (en) | 1988-11-04 |
Family
ID=14131837
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57095226A Granted JPS58212101A (en) | 1982-06-03 | 1982-06-03 | Moisture sensor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58212101A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3026791U (en) * | 1995-09-18 | 1996-07-23 | 秀次 中村 | Flowerpot with holes only on the side |
-
1982
- 1982-06-03 JP JP57095226A patent/JPS58212101A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3026791U (en) * | 1995-09-18 | 1996-07-23 | 秀次 中村 | Flowerpot with holes only on the side |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58212101A (en) | 1983-12-09 |
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