JPS6355765B2 - - Google Patents
Info
- Publication number
- JPS6355765B2 JPS6355765B2 JP57036373A JP3637382A JPS6355765B2 JP S6355765 B2 JPS6355765 B2 JP S6355765B2 JP 57036373 A JP57036373 A JP 57036373A JP 3637382 A JP3637382 A JP 3637382A JP S6355765 B2 JPS6355765 B2 JP S6355765B2
- Authority
- JP
- Japan
- Prior art keywords
- humidity
- moisture
- sensitive
- present
- sensitive resistor
- 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
- 239000000203 mixture Substances 0.000 claims description 20
- 229910052788 barium Inorganic materials 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052712 strontium Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 229910052745 lead Inorganic materials 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000007789 gas Substances 0.000 description 19
- 238000001514 detection method Methods 0.000 description 14
- 238000001354 calcination Methods 0.000 description 7
- 239000000919 ceramic Substances 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 6
- 238000010304 firing Methods 0.000 description 6
- 230000035945 sensitivity Effects 0.000 description 6
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 239000011521 glass Substances 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000011133 lead Substances 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- 238000005467 ceramic manufacturing process Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000009766 low-temperature sintering Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Non-Adjustable Resistors (AREA)
Description
本発明は、感湿抵抗体組成物に係り、特に耐腐
食性ガスに侵されず、また、広い湿度範囲にわた
つて高い湿度センシイテイビテイを示し、かつ直
線性、安定性、再現性に優れた感湿抵抗体組成物
に関するものである。
感湿素子は、感湿部分を測定雰囲気に直接暴露
した状態で使用するので、種々の汚染環境にさら
される。感湿素子は、このような環境下でも感湿
材料が劣化して、特性の経時ドリフトがあつては
ならない。
感湿素子を空調機の湿度検出に利用する場合感
湿材料を汚染したり劣化したりするものは、
(1) 温泉地に近い場所で常に存在するH2Sを含ん
だ環境
(2) 交通量の多い交差点付近で自動車から放出さ
れる排気ガス中に含まれるNO2やSO2を含んだ
環境
があげられる。
感湿素子は、このような悪環境下においても特
性の経時ドリフトがあつてはならない。
従来、金属酸化物系の感湿抵抗体材料として
は、Ni1-xFe2+xO4セラミツク、Fe2O3−K2Oセラ
ミツクMgCr2O4−TiO2セラミツク等が知られて
いる。これらのセラミツクは、いずれもH2S、
SO2、NO2等の腐食性ガスによつてセラミツクの
表面が侵されて特性がドリフトし、時間が経つに
つれて湿度検出誤差が大きくなるという重大な欠
点をもつ。のみならず、これらのセラミツクは焼
成温度が高いため、通常の厚膜工程では焼結させ
ることができず、結合剤としてガラスバインダを
用いる必要がある。
しかし、ガラスバインダを用いると感湿素子は
感度が低下し、抵抗値が大きくなり、これらの材
料で厚膜感湿素子は形成できない。したがつて、
厚膜技術の採用による量産性の向上、価格の低減
および素子精度の向上が実現できない。
このような事情から、現在のところ使用環境が
きびしく、かつ比較的精度を必要とする空調設備
の分野においては、金属酸化物系の厚膜湿度セン
サは実用化されていない。
本発明の目的は、上記した従来技術の欠点をな
くし、腐食性ガスに対して材料が侵かされずまた
1000℃以下の低温焼結で厚膜形成するという要求
に合致し、長寿命であり、高感度でありかつ低価
格な感湿抵抗体組成物を提供することにある。
本発明者らは、すでに1000℃以下の低温焼結を
実現し、湿度変化に対する抵抗値変化が大きく、
かつ吸湿時の抵抗値が小さい感湿抵抗体組成物と
して、ヒユブネライト型あるいはシーライト型の
金属酸化物NWO4（Ｍは、Mn、Co、Fe、Ni、
Mg、Ca、Ba、Sr、Zn、Pbの少なくとも一種の
金属）をガラスバインダを用いずに厚膜化するこ
とを提案した。
本発明者らは、さらに腐食性ガスによる材料の
劣化を防ぐために、添加物の探索を進めた。
この結果、上記組成物に五酸化バナジウムを含
有せしめた感湿抵抗体組成物は、腐食性ガスに侵
されにくいことをみい出した。したがつてH2S、
NO2、SO2等の腐食性ガスに暴露させても抵抗値
のドリフトがほとんど生じない。
図はMnWO4100重量部にV2O5を10重量部添加
した感湿抵抗体を、H2S：0.5ppm、SO2：
1ppmNO2：1ppm、温度30℃、湿度75％RHの腐
食性ガス雰囲気中に放置したときの24℃、50％
RHにおける湿度検出誤差の経時変化を示したも
のである。V2O5を添加しないもの１は時間が経
つにつれて湿度検出誤差が大きくなり、200時間
で10％RH以上の湿度検出誤差を生じる。しか
し、V2O5を添加したもの２は200時間でわずか２
％RH以内の湿度検出誤差で、V2O5の添加により
きわめて耐腐食ガス性が向上することがわかる。
このようにV2O5の添加によつて腐食性ガスに
対する耐久性が向上した理由は、感湿部表面のマ
ンガンサイトが腐食性ガスと反応しにくいバナジ
ウムによつて置換されたためと考えられる。
本発明にかかる感湿抵抗体組成物は、ヒユブネ
ライト型あるいはシーライト型の金属酸化物
MWO4（Ｍは、Mn、Co、Fe、Ni、Mg、Ca、
Ba、Sr、Zn、Pbの少なくとも一種の金属）100
重量部と、五酸化バナジウム（V2O5）0.5〜30重
量部よりなるものである。
この感湿抵抗体組成物は、腐食性ガスを含む雰
囲気に暴露しても特性がほとんど変化せず、かつ
湿度変化による抵抗値変化が大きく、直線的に変
化をする。
また、感湿部はバインダガラスを含まないので
1000℃以下の低温で焼結でき、かつ感度低下や素
子抵抗値増加が起らないので、量産性がよく、低
価格な感湿素子を供給できる。
次に本発明においてV2O5含有量を上記のごと
く限定した理由についてのべる。V2O5が0.5重量
部より少なくすると、腐食性ガスの暴露によつて
生じる特性の変化が著しく大きくなり、湿度の検
出誤差が大きくなる。また、V2O5の添加量が30
重量部を越えると、湿度変化に対する抵抗値変化
が小さくなり、湿度検出精度が劣るという欠点を
生じる。
本発明の感湿抵抗体組成物は、通常のセラミツ
ク製造プロセスによつて製造できる。すなわち、
原料としてマンガン、コバルト、鉄、ニツケル、
マグネシウム、バリウム、カルシウム、ストロン
チウム、亜鉛、鉛、タングステン、パナジウムの
酸化物を用い、組成に応じてこれら原料を所定の
割合で秤量し、通常の混合法、例えばらいかい
機、ホールミルにより充分混合する。
混合物は、600〜850℃の温度で空気中で仮焼成
する。850℃より高温での仮焼は、この組成物中
の五酸化パナジウムの蒸発を生じるので好ましく
ない。また、650℃より低温での焼成では仮焼成
が充分でないので好ましくない。
仮焼の焼成時間は、ヒユブネライトあるいはシ
ーライトの構成元素、仮焼温度に依存する。より
低い仮焼温度では、より長い時間の仮焼が通常行
われる。通常の仮焼の焼成時間は0.5〜８時間で
ある。
仮焼した後、仮焼成物をらいかい機、ボールミ
ル等で粉砕し、所望の粒径をもつた粉末を得るこ
とができる。通常、仮焼成物は粉砕によりすべて
の粒子が最大粒径において20μ以下になるように
する。
このようにして粉砕した仮焼粉末を通常のプレ
ス技術によりデイスクとし、焼成させる。それに
より得られた焼結体に、例えばRuO2ペーストを
使用して電極を形成し、セラミツク型感湿素子を
製造することができる。
また、本発明の感湿抵抗体組成物は、厚膜感湿
素子に適用できる。
以下に本発明を実施例につき詳細に説明すると
ともに比較例を掲げて本発明の効果を示す。
原料として、酸化マンガン（Mn3O4）、酸化ニ
ツケル（NiO）、酸化鉄（Fe2O3）、酸化マグネシ
ウム（MgO）、酸化カルシウム（CaO）酸化バリ
ウム（BaO）、酸化亜鉛（PbO）、酸化亜鉛
（ZnO）、酸化タングステン（WO3）および酸化
バナジウム（V2O5）中より焼成物が所定の組成
物になるように秤量し、アルミナ製ポツトミルで
湿式混合した。
混合物を白金るつぼに入れて、630〜830℃の温
度で１〜２時間仮焼した。この仮焼物をメノー製
ボールミルで４〜16時間粉砕した後、その粉末20
ｇに対し約１mlの３％PVA溶液をバインダとし
て加え、約1.5ton／cm2の圧力で直径15mm厚さ0.3
mmの円板に形成し、これを約800〜900℃の温度で
２時間焼成し、焼結体を得た。
得られた焼結体にRuO2電極を形成し、電気的
諸特性の測定試料とした。
このようにして作成した試料を、H2S：
0.5ppm、SO2：1ppm、NO2：1ppm、温度30℃、
湿度75％RHの腐食性ガス雰囲気中に200時間暴
露した後50％RHにおける抵抗値変化を測定し、
これに相当する湿度検出誤差を求めた。
表は、感湿抵抗体組成物の代表的実施例No.１〜
26、および比較例No.１〜５の組成、焼結温度焼結
時間、感度および湿度検出誤差である。
表から明らかなように、本発明の感湿抵抗体組
成物、すなわちV2O5含有量が好ましい0.5〜30重
量部の範囲にあるもの（No.１〜26）で作成した感
湿素子は、腐食性ガス暴露により生じる湿度検出
誤差が少なく、10％RH以下である。しかも感湿
感度が5000以上ときわめて高く、かつ直線性にす
ぐれている。これに対して添加物の含有量が0.5
重量部より少ないものは、腐食性ガス暴露により
生じる湿度検出誤差が10％RH以上となり、湿度
検出精度が悪くなる。また、添加物の含有量が30
重量部より多いものは、感度5000以下に低下し、
かつ、直線性も悪くなるため、湿度計測上障害と
なる。
The present invention relates to a humidity-sensitive resistor composition, which is particularly uncorrosive to corrosive gases, exhibits high humidity sensitivity over a wide humidity range, and has excellent linearity, stability, and reproducibility. The present invention relates to a moisture-sensitive resistor composition. Moisture sensing elements are used with the humidity sensing portion directly exposed to the measurement atmosphere, so they are exposed to various contaminated environments. Even under such an environment, the moisture-sensitive material of the moisture-sensitive element must not deteriorate and its characteristics must not drift over time. When using a humidity-sensitive element to detect humidity in an air conditioner, the following things can contaminate or deteriorate the humidity-sensitive material: (1) Environments containing H 2 S, which are always present near hot spring areas (2) Traffic An example of this is an environment containing NO 2 and SO 2 contained in the exhaust gas emitted from cars near busy intersections. The moisture-sensitive element must not have characteristics that drift over time even under such adverse environments. Ni 1-x Fe 2+x O 4 ceramic, Fe 2 O 3 −K 2 O ceramic, MgCr 2 O 4 −TiO 2 ceramic, etc. are conventionally known as metal oxide-based moisture-sensitive resistor materials. . These ceramics all contain H 2 S,
This has the serious drawback that the surface of the ceramic is attacked by corrosive gases such as SO 2 and NO 2 , causing the characteristics to drift and the humidity detection error to increase over time. Furthermore, since these ceramics have a high firing temperature, they cannot be sintered in a normal thick film process, and it is necessary to use a glass binder as a binding agent. However, when a glass binder is used, the sensitivity of the moisture sensitive element decreases and the resistance value increases, so that a thick film moisture sensitive element cannot be formed using these materials. Therefore,
It is not possible to improve mass productivity, reduce costs, and improve device precision by adopting thick film technology. For these reasons, metal oxide-based thick film humidity sensors have not been put into practical use at present in the field of air conditioning equipment, which is used in harsh environments and requires relatively high accuracy. The object of the present invention is to eliminate the above-mentioned drawbacks of the prior art and to prevent materials from being attacked by corrosive gases.
The object of the present invention is to provide a moisture-sensitive resistor composition that meets the requirement of forming a thick film by sintering at a low temperature of 1000°C or less, has a long life, is highly sensitive, and is inexpensive. The present inventors have already achieved low-temperature sintering of 1000℃ or less, and the resistance value changes greatly with humidity changes.
As a moisture-sensitive resistor composition having a small resistance value when absorbing moisture, a hyubnerite-type or sealite-type metal oxide NWO 4 (M is Mn, Co, Fe, Ni,
We proposed to thicken the film of at least one metal (Mg, Ca, Ba, Sr, Zn, Pb) without using a glass binder. The present inventors further investigated additives to prevent material deterioration due to corrosive gases. As a result, it was found that the moisture-sensitive resistor composition containing vanadium pentoxide in the above composition is less susceptible to corrosive gases. Therefore H 2 S,
Even when exposed to corrosive gases such as NO 2 and SO 2 , there is almost no drift in resistance value. The figure shows a moisture-sensitive resistor made by adding 10 parts by weight of V 2 O 5 to 100 parts by weight of MnWO 4 , H 2 S: 0.5 ppm, SO 2 :
1ppmNO2 : 1ppm, 24℃, 50% when left in a corrosive gas atmosphere with a temperature of 30℃ and a humidity of 75%RH
This figure shows the change in humidity detection error over time at RH. In case 1 in which V 2 O 5 is not added, the humidity detection error increases over time, resulting in a humidity detection error of 10% RH or more after 200 hours. However, V 2 O 5 -added version 2 produces only 2 in 200 hours.
It can be seen that the addition of V 2 O 5 significantly improves corrosion gas resistance with a humidity detection error within %RH. The reason why the durability against corrosive gases was improved by the addition of V 2 O 5 is thought to be that the manganese sites on the surface of the moisture sensitive part were replaced by vanadium, which is less likely to react with corrosive gases. The moisture sensitive resistor composition according to the present invention comprises a hyubnerite type or sealite type metal oxide.
MWO 4 (M is Mn, Co, Fe, Ni, Mg, Ca,
At least one metal of Ba, Sr, Zn, Pb) 100
parts by weight and 0.5 to 30 parts by weight of vanadium pentoxide (V 2 O 5 ). The characteristics of this moisture-sensitive resistor composition hardly change even when exposed to an atmosphere containing a corrosive gas, and the resistance value changes largely and linearly due to changes in humidity. In addition, the moisture sensing part does not contain binder glass.
Since it can be sintered at a low temperature of 1000°C or less and does not cause a decrease in sensitivity or an increase in element resistance, it is easy to mass produce and can provide low-cost moisture-sensitive elements. Next, the reason why the V 2 O 5 content is limited as described above in the present invention will be described. When V 2 O 5 is less than 0.5 part by weight, changes in properties caused by exposure to corrosive gases become significantly large, and humidity detection errors become large. Also, the amount of V 2 O 5 added is 30
If it exceeds the weight part, the change in resistance value with respect to changes in humidity will be small, resulting in a disadvantage that humidity detection accuracy will be poor. The moisture sensitive resistor composition of the present invention can be manufactured by a conventional ceramic manufacturing process. That is,
Raw materials include manganese, cobalt, iron, nickel,
Using oxides of magnesium, barium, calcium, strontium, zinc, lead, tungsten, and panadium, these raw materials are weighed in a predetermined ratio according to the composition, and thoroughly mixed using a normal mixing method, such as a sieve or a whole mill. . The mixture is calcined in air at a temperature of 600-850°C. Calcining at temperatures higher than 850°C is undesirable as it results in evaporation of the panadium pentoxide in the composition. Further, firing at a temperature lower than 650° C. is not preferable because preliminary firing is insufficient. The firing time for calcination depends on the constituent elements of hyubnerite or celite and the calcination temperature. At lower calcination temperatures, longer calcination times are typically performed. The firing time for normal calcination is 0.5 to 8 hours. After calcining, the calcined product is pulverized using a mill, a ball mill, etc. to obtain a powder having a desired particle size. Normally, the calcined product is pulverized so that all particles have a maximum particle size of 20 μm or less. The thus pulverized calcined powder is formed into a disk by a conventional pressing technique and fired. Electrodes can be formed on the resulting sintered body using, for example, RuO 2 paste to produce a ceramic moisture-sensitive element. Further, the humidity-sensitive resistor composition of the present invention can be applied to a thick-film moisture-sensitive element. EXAMPLES Below, the present invention will be explained in detail with reference to examples, and comparative examples will be given to demonstrate the effects of the present invention. Raw materials include manganese oxide (Mn 3 O 4 ), nickel oxide (NiO), iron oxide (Fe 2 O 3 ), magnesium oxide (MgO), calcium oxide (CaO), barium oxide (BaO), zinc oxide (PbO), Zinc oxide (ZnO), tungsten oxide (WO 3 ), and vanadium oxide (V 2 O 5 ) were weighed out so that the fired product would have a predetermined composition, and wet mixed in an alumina pot mill. The mixture was placed in a platinum crucible and calcined for 1 to 2 hours at a temperature of 630 to 830°C. After grinding this calcined material in an agate ball mill for 4 to 16 hours, the powder
Add about 1 ml of 3% PVA solution to each g as a binder, and apply a pressure of about 1.5 ton/cm 2 to form a mold with a diameter of 15 mm and a thickness of 0.3 mm.
A sintered body was obtained by forming a disc of 1 mm in diameter and firing it at a temperature of about 800 to 900°C for 2 hours. A RuO 2 electrode was formed on the obtained sintered body, and it was used as a sample for measuring various electrical properties. The sample prepared in this way was mixed with H 2 S:
0.5ppm, SO 2 : 1ppm, NO 2 : 1ppm, temperature 30℃,
After being exposed to a corrosive gas atmosphere with a humidity of 75% RH for 200 hours, we measured the change in resistance value at 50% RH.
The humidity detection error corresponding to this was determined. The table shows representative examples No. 1 to 1 of humidity-sensitive resistor compositions.
26, and the composition, sintering temperature, sintering time, sensitivity, and humidity detection error of Comparative Examples Nos. 1 to 5. As is clear from the table, the moisture-sensitive elements made with the humidity-sensitive resistor compositions of the present invention, that is, those whose V 2 O 5 content is preferably in the range of 0.5 to 30 parts by weight (Nos. 1 to 26) , the humidity detection error caused by exposure to corrosive gas is small, less than 10% RH. Moreover, it has an extremely high moisture sensitivity of over 5000, and excellent linearity. In contrast, the content of additives is 0.5
If the amount is less than parts by weight, the humidity detection error caused by exposure to corrosive gas will be 10%RH or more, resulting in poor humidity detection accuracy. In addition, the content of additives is 30
If the amount is more than parts by weight, the sensitivity will drop to less than 5000,
In addition, linearity also deteriorates, which poses a problem in humidity measurement.
【表】【table】
【表】
以上述べたように、本発明による感湿抵抗体組
成物は腐食性ガスにより侵かされないため、腐食
性ガスを含んだ環境下で使用してもほとんど特性
がドリフトせず、湿度検出誤差はきわめて小さ
い。
また、湿度に対して抵抗値が直線的に変化しか
つ湿度変化に対する抵抗変化が大きく、その再現
性が良く、抵抗値の経時変化が全くみられず、極
めて安定であり、感応速度が非常に速いという特
徴を有する。[Table] As mentioned above, since the humidity-sensitive resistor composition according to the present invention is not attacked by corrosive gases, its characteristics hardly drift even when used in an environment containing corrosive gases, and humidity detection The error is extremely small. In addition, the resistance value changes linearly with humidity, and the resistance change with humidity changes is large, the reproducibility is good, there is no change in resistance value over time, it is extremely stable, and the response speed is extremely high. It has the characteristic of being fast.
図は本発明にかかる感湿素子および比較例の感
湿素子を腐食性ガス中に放置したときの湿度検出
誤差の経時変化を示す図。
１……V2O5を添加しないもの、２……V2O5を
添加したもの。
The figure is a diagram showing changes over time in humidity detection errors when a humidity sensing element according to the present invention and a humidity sensing element of a comparative example are left in a corrosive gas. 1... V 2 O 5 is not added, 2... V 2 O 5 is added.
Claims (1)
Ni、Mg、Ba、Ca、Sr、Zn、Pbから選ばれた少
くとも一種の金属）100重量部と、V2O5を0.5〜
30重量部よりなることを特徴とする感湿抵抗体組
成物。1 MWO 4 (However, in the formula, M is Mn, Co, Fe,
100 parts by weight of at least one metal selected from Ni, Mg, Ba, Ca, Sr, Zn, Pb and 0.5 to 0.5 parts by weight of V 2 O 5
A moisture-sensitive resistor composition comprising 30 parts by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57036373A JPS58154201A (en) | 1982-03-10 | 1982-03-10 | Moisture sensitive resistor composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57036373A JPS58154201A (en) | 1982-03-10 | 1982-03-10 | Moisture sensitive resistor composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58154201A JPS58154201A (en) | 1983-09-13 |
| JPS6355765B2 true JPS6355765B2 (en) | 1988-11-04 |
Family
ID=12468032
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57036373A Granted JPS58154201A (en) | 1982-03-10 | 1982-03-10 | Moisture sensitive resistor composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58154201A (en) |
-
1982
- 1982-03-10 JP JP57036373A patent/JPS58154201A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58154201A (en) | 1983-09-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4357426A (en) | Humidity sensitive ceramics | |
| JPS6355765B2 (en) | ||
| US4509035A (en) | Humidity-sensitive element and process for producing the same | |
| EP0045950A2 (en) | Moisture sensitive element | |
| EP0123385B1 (en) | Humidity-sensitive resistive element | |
| JPS639722B2 (en) | ||
| KR910001859B1 (en) | Humidity-sensing component composition | |
| JPS6355846B2 (en) | ||
| KR840000260B1 (en) | Temperature-responsive element | |
| JP3559911B2 (en) | Thermistor | |
| JPS6072201A (en) | Moisture sensitive resistor composition | |
| JPS60158601A (en) | Moisture sensitive resistor composition | |
| JPH0828283B2 (en) | Moisture sensitive element composition | |
| JPS63194307A (en) | Humidity sensitive ceramics | |
| JPS6252921B2 (en) | ||
| JPS6041841B2 (en) | moisture sensing element | |
| JPH0543161B2 (en) | ||
| JPS60192301A (en) | Moisture sensitive resistor composition | |
| JPS635882B2 (en) | ||
| JPS5951336A (en) | Alcohol gas detecting element | |
| JPH0318721B2 (en) | ||
| JPS5832303A (en) | Humidity sensitive dielectric loss element | |
| JPS6161242B2 (en) | ||
| JPS5813003B2 (en) | Kanshitsusoshi | |
| JPS62108503A (en) | Oxide semiconductor for thermistor |