JPS635882B2 - - Google Patents
Info
- Publication number
- JPS635882B2 JPS635882B2 JP58014902A JP1490283A JPS635882B2 JP S635882 B2 JPS635882 B2 JP S635882B2 JP 58014902 A JP58014902 A JP 58014902A JP 1490283 A JP1490283 A JP 1490283A JP S635882 B2 JPS635882 B2 JP S635882B2
- Authority
- JP
- Japan
- Prior art keywords
- humidity
- mol
- tio
- resistance
- component
- 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
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 description 14
- 229910010413 TiO 2 Inorganic materials 0.000 description 13
- 229910052573 porcelain Inorganic materials 0.000 description 10
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 150000004706 metal oxides Chemical class 0.000 description 6
- 230000035945 sensitivity Effects 0.000 description 6
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229910001120 nichrome Inorganic materials 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000010411 cooking Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- -1 V 2 O 3 Inorganic materials 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Non-Adjustable Resistors (AREA)
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Description
本発明はACr2O4―TiO2（ただしＡはFe，Ni，
Co，MnおよびCuのうちから選ばれた少なくと
も１種）系磁器からなる湿度検出素子に関するも
のである。
一般に感湿抵抗体は湿度に敏感に感応し、湿度
によつてその抵抗値が変化する抵抗体であり、湿
度測定用の素子や湿度調節用のセンサとして使用
されている。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、水分の吸脱現象
によつて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。したが
つて、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、導電性の物質、
たとえばカーボンを添加混合することが試られて
いる。しかしながら、この方法では、抵抗の絶対
値は低くなるものの、湿度変化に対する抵抗変化
量がいちじるしく減少してしまい、実際にこれを
使用することはむずかしい。
さらにまた、感湿抵抗体素子の応用分野とし
て、最近、食品の加工、調理の分野が注目されて
いる。この分野においては雰囲気の温度上昇があ
り、それに伴つて相対湿度の低下が往々にして見
受けられ、低湿度領域での使用の可能なものが必
要とされている。かかる用途には、従来の金属酸
化物感湿抵抗体素子を使用することができなかつ
た。
本発明は、かかる問題点を解決することができ
たもので、これまでの材料とは異なる新しい金属
酸化物系磁器組成物を提供しようとするものであ
る。すなわち、本発明にかかる磁器組成物は、
ACr2O4成分（ただしＡはFe，Ni，Co，Mn，Cu
のうちから選ばれた少なくとも１種）１〜99モル
％と、TiO2成分99〜１モル％とを含むことを特
徴とする。上記組成比率の成分、またはそれを主
体とする成分の磁器に電極を付与すると、湿度に
応じて電極間の抵抗が決まる。その組成を選ぶこ
とにより、低湿度領域においても高い感度を示す
素子を得ることができる。
さらに詳細に述べるならば、本発明にかかる湿
度検出素子は、一種の半導体であり、その組成を
選定することによつてかなり低い抵抗の感温感湿
特性を示す湿度検出素子を作ることができる。し
かも、ACr2O4（ただしＡはFe，Ni，Co，Mn，
およびCuのうちから選ばれた少なくとも１種）
はスピネル型結晶構造の化合物であり、このスピ
ネル系とTiO2系の二相形の磁器であることも原
因して、その抵抗温度係数が小さく、特に温度補
償をする必要性もない。このため、比較例インピ
ーダンスの低い回路を用いて、容易に相対湿度０
〜100％の全湿度領域において検出でき、さらに
またその応答性も早いものである。
そして、本発明にかかる磁器組成物は、通常の
磁器製造技術で簡単に製造することができるもの
であり、現用の製造設備を用いて容易に量産する
ことができる。さらに、これはいわゆる金属酸化
物高温焼結体であり、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。従来使用さ
れていた金属酸化物は、その表面状態がきわめて
変化しやすいものであり、これに比較して本発明
にかかる磁器組成物に特性的に安定している。し
たがつて、長寿命であり、高温度下においても湿
度の測定をすることができる。
ACr2O4（ただしＡはFe，Ni，Co，Mnおよび
Cuのうちから選ばれた少なくとも１種）成分と、
TiO2成分との組成比において前者が１モル％よ
り少なく、後者が99モル％より多いと、湿度変化
に対する抵抗変化がほとんどなくなる。さらに前
者が99モル％より多くなり、後者が１モル％より
少なくなると、TiO2成分の添加効果が顕著でな
くなり、低湿度領域での高い感度を得ることがで
きなくなる。
以下本発明にかかる磁器組成物の具体例につい
て、NiCr2O4―TiO2系を代表させて説明する。
まず99.99％以上のNiO，Cr2O3，およびTiO2を
準備し、これを下表の組成比になるように配合し
て、メノウボール入りボツトミルで湿式混合し
た。
The present invention is based on ACr 2 O 4 --TiO 2 (where A is Fe, Ni,
The present invention relates to a humidity detection element made of at least one type of porcelain selected from Co, Mn, and Cu. In general, a humidity-sensitive resistor is a resistor that is sensitive to humidity and whose resistance value changes depending on the humidity, and is used as a humidity measurement element or a humidity adjustment sensor. As is well known, Fe 2 O 3 , Al 2 O 3 ,
Metal oxides such as Cr 2 O 3 and Ni 2 O 3 have excellent water absorption properties, and therefore, moisture-sensitive resistor elements are manufactured using such properties. 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 the phenomenon of absorption and removal of moisture, it is difficult to accurately detect this electrically. It is something. Therefore, this type of device is limited to applications in high humidity areas, such as detection of dew point, for example. In order to make an element with a resistance value that is easy to measure, conductive substances,
For example, attempts have been made to add and mix carbon. However, although this method lowers the absolute value of resistance, the amount of change in resistance with respect to changes in humidity is significantly reduced, making it difficult to actually use this method. Furthermore, the fields of food processing and cooking have recently been attracting attention as application fields for humidity-sensitive resistor elements. In this field, as the temperature of the atmosphere increases, the relative humidity often decreases, and there is a need for a device that can be used in a low humidity region. Conventional metal oxide moisture sensitive resistor elements cannot be used for such applications. The present invention has been able to solve these problems and aims to provide a new metal oxide-based ceramic composition that is different from conventional materials. That is, the porcelain composition according to the present invention is
ACr 2 O 4 components (A is Fe, Ni, Co, Mn, Cu
It is characterized by containing 1 to 99 mol % of at least one selected from the group consisting of 1 to 99 mol % of TiO 2 component and 99 to 1 mol % of TiO 2 component. When electrodes are applied to porcelain having the above-mentioned composition ratio or a component mainly composed of the same, the resistance between the electrodes is determined depending on the humidity. By selecting the composition, it is possible to obtain an element that exhibits high sensitivity even in a low humidity region. More specifically, the humidity sensing element according to the present invention is a type of semiconductor, and by selecting its composition, it is possible to create a humidity sensing element that exhibits temperature- and humidity-sensitive characteristics with considerably low resistance. . Furthermore, ACr 2 O 4 (where A is Fe, Ni, Co, Mn,
and at least one selected from Cu)
is a compound with a spinel crystal structure, and because it is a two-phase porcelain consisting of spinel and TiO 2 systems, its temperature coefficient of resistance is small, and there is no need for any particular temperature compensation. Therefore, using a circuit with low impedance in the comparative example, it is possible to easily reduce the relative humidity to 0.
It can be detected in all humidity ranges up to 100%, and its response is also fast. The porcelain composition according to the present invention can be easily manufactured using ordinary porcelain manufacturing techniques, and can be easily mass-produced using current manufacturing equipment. Furthermore, this is a so-called high-temperature sintered metal oxide, and its surface condition does not change even if it is left in the atmosphere for a long period of time. The surface conditions of conventionally used metal oxides are extremely susceptible to change, and in comparison, the properties of the ceramic composition according to the present invention are stable. Therefore, it has a long life and can measure humidity even under high temperatures. ACr 2 O 4 (where A is Fe, Ni, Co, Mn and
At least one component selected from Cu);
When the composition ratio with the TiO 2 component is less than 1 mol % of the former and more than 99 mol % of the latter, there is almost no change in resistance against changes in humidity. Further, if the former becomes more than 99 mol% and the latter becomes less than 1 mol%, the effect of adding the TiO 2 component becomes insignificant, making it impossible to obtain high sensitivity in a low humidity region. Specific examples of the ceramic composition according to the present invention will be described below, using the NiCr 2 O 4 --TiO 2 system as a representative example.
First, 99.99% or more of NiO, Cr 2 O 3 , and TiO 2 were prepared, mixed in a composition ratio as shown in the table below, and wet-mixed in a bottom mill containing an agate ball.
【表】
混合物を乾燥させてから、３％ポリビニルアル
コール水溶液を、混合粉末100ｇに対して10c.c.の
割合で加え、乳鉢で混合して造粒した。そして
750Kg／cm2の圧力で10mm×5.5mm×0.25mmの角板状
に成型した。この成型体を空気中において1300℃
の温度で２時間保持して焼成した。このようにし
て得られた磁器にRuO2を含むペーストをスクリ
ーンメツシユ法で櫛型状に印刷して、さらに800
℃の温度で焼成し、１対の電極を形成した。第１
図にその構成を示す。第１図ａは側面図、第１図
ｂは斜視図である。第１図において試料面１，２
に櫛形状電極３と側面に導通電極（RUO2系）を
設けた。導通電極は、一面に焼付けた櫛形状電極
と、他面に焼付けた櫛形状電極を並列になるよう
に導通するための電極である。４は電極端子取出
用リード線である。
次に、このようにして得た試料１〜６の相対湿
度―抵抗特性を測定雰囲気の相対湿度を変化させ
て各試料の電極間の抵抗を測定することによつて
調べた。その結果を第２図に示す。図に付した符
号は、試料番号に対応させている。
図から明らかなように、NiCr2O4に対する
TiO2の量が多くなるに従つて、全般的に抵抗が
低下し、かつ低湿度領域の感度が高くなる。そし
てTiO2の量が増すと、相対湿度―抵抗特性が直
線的になる。それをすぎると湿度変化に対して感
度はほとんど得られなくなる。すなわち、試料２
のようにNiCrO4成分が99％でTiO2成分が１モル
％のとき、その低湿度領域での感度が高い。とこ
ろが、Tio2成分が１モル％より少ないと、ほぼ
試料１と同じ特性になることが認められた。
TiO2成分が１モル％以上になると磁器が二相形
となつていることが明らかに認められた。TiO2
成分が99モル％より多くなると、試料６から明ら
かなようにNiCr2O4による効果が得られず、実用
的でない。
以上、NiCr2O4―TiO2系について説明したが、
他の系についてもほとんど同じ相対湿度―抵抗特
性が認められた。
以上のように本発明にかかる湿度検出素子は、
ACr2O4成分（ただしＡはFe，Ni，Co，Mn，お
よびCuのうちから選ばれた少なくとも１種）１
〜99モル％とTiO2成分99〜１モル％とからなる
磁器の感湿特性を利用するものである。この素子
は、０〜100％の相対湿度領域において高い感度
を示し、その組成比を選ぶことにより希望する特
性のものが得られる。この磁器は1300℃という高
温度にも耐えることができるので、この素子は高
温度下で使用することがき、高温高湿度下での使
用によつても特性劣化のきわめて少ないものであ
る。このため食品の加工、調理の分野などでの湿
度センサとしてあるいは空気調整システムなどに
有用なものである。
なお本発明において他の成分をさらに導入して
特性などの改善をはかることも可能である。たと
えば、SiO2，Al2O3，V2O3，Bi2O3などを鉱化剤
として添加して焼結性を改善することができる。[Table] After the mixture was dried, a 3% polyvinyl alcohol aqueous solution was added at a ratio of 10 c.c. to 100 g of mixed powder, and the mixture was mixed in a mortar and granulated. and
It was molded into a rectangular plate shape of 10 mm x 5.5 mm x 0.25 mm under a pressure of 750 Kg/cm 2 . This molded body was placed in air at 1300℃.
It was held at a temperature of 2 hours for firing. A paste containing RuO 2 was printed on the porcelain thus obtained in a comb shape using a screen mesh method, and an additional 800
℃ temperature to form a pair of electrodes. 1st
The configuration is shown in the figure. FIG. 1a is a side view, and FIG. 1b is a perspective view. In Figure 1, sample surfaces 1 and 2
A comb-shaped electrode 3 and a conductive electrode (RUO 2 system) were installed on the side. The conduction electrode is an electrode for electrically connecting a comb-shaped electrode baked on one side and a comb-shaped electrode baked on the other side in parallel. 4 is a lead wire for taking out an electrode terminal. Next, the relative humidity-resistance characteristics of Samples 1 to 6 thus obtained were investigated by varying the relative humidity of the measurement atmosphere and measuring the resistance between the electrodes of each sample. The results are shown in FIG. The symbols attached to the figures correspond to the sample numbers. As is clear from the figure, for NiCr 2 O 4
As the amount of TiO 2 increases, the overall resistance decreases and the sensitivity in the low humidity region increases. And as the amount of TiO 2 increases, the relative humidity-resistance characteristic becomes linear. If it exceeds this value, almost no sensitivity to humidity changes can be obtained. That is, sample 2
When the NiCrO 4 component is 99% and the TiO 2 component is 1 mol%, the sensitivity is high in that low humidity region. However, it was found that when the Tio 2 component was less than 1 mol %, the properties were almost the same as those of Sample 1.
It was clearly observed that when the TiO 2 component was 1 mol % or more, the porcelain became two-phase. TiO2
If the content of the component exceeds 99 mol%, as is clear from Sample 6, the effect of NiCr 2 O 4 cannot be obtained and is not practical. The NiCr 2 O 4 -TiO 2 system has been explained above, but
Almost the same relative humidity-resistance characteristics were observed for the other systems. As described above, the humidity detection element according to the present invention is
ACr 2 O 4 components (A is at least one selected from Fe, Ni, Co, Mn, and Cu) 1
It utilizes the moisture-sensitive properties of porcelain, which consists of ~99 mol% and 99-1 mol% of TiO2 components. This element exhibits high sensitivity in the relative humidity range of 0 to 100%, and desired characteristics can be obtained by selecting the composition ratio. Since this porcelain can withstand temperatures as high as 1,300°C, this element can be used at high temperatures and exhibits extremely little characteristic deterioration even when used at high temperatures and high humidity. Therefore, it is useful as a humidity sensor in the fields of food processing and cooking, or in air conditioning systems. In the present invention, it is also possible to further introduce other components to improve properties. For example, SiO 2 , Al 2 O 3 , V 2 O 3 , Bi 2 O 3 and the like can be added as mineralizers to improve sinterability.
第１図ａ，ｂはそれぞれ本発明の一実施例の湿
度検出素子の側面図、斜視図、第２図はその相対
湿度―抵抗特性曲線図である。
１，２……試料面、３……櫛形状電極、４……
リード線。
FIGS. 1a and 1b are a side view and a perspective view, respectively, of a humidity detecting element according to an embodiment of the present invention, and FIG. 2 is a relative humidity-resistance characteristic curve thereof. 1, 2...sample surface, 3...comb-shaped electrode, 4...
Lead.
Claims (1)
およびCuのうちから選ばれた少なくとも１種）
１〜99モル％と、TiO2成分99〜１モル％を含む
焼結体からなる湿度検出素子。1 ACr 2 O 4 components (A is Fe, Ni, Co, Mn
and at least one selected from Cu)
A humidity sensing element made of a sintered body containing 1 to 99 mol% of TiO2 component and 99 to 1 mol% of TiO2 component.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58014902A JPS58130501A (en) | 1983-01-31 | 1983-01-31 | Humidity detection element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58014902A JPS58130501A (en) | 1983-01-31 | 1983-01-31 | Humidity detection element |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58130501A JPS58130501A (en) | 1983-08-04 |
| JPS635882B2 true JPS635882B2 (en) | 1988-02-05 |
Family
ID=11873917
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58014902A Granted JPS58130501A (en) | 1983-01-31 | 1983-01-31 | Humidity detection element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58130501A (en) |
-
1983
- 1983-01-31 JP JP58014902A patent/JPS58130501A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58130501A (en) | 1983-08-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4357426A (en) | Humidity sensitive ceramics | |
| CA1045249A (en) | Humidity sensitive ceramic resistor | |
| US4464647A (en) | Humidity sensor made of metal oxide | |
| Ishihara et al. | Capacitive-type gas sensor for the selective detection of carbon dioxide | |
| JP4548431B2 (en) | Thermistor composition and thermistor element | |
| JPS635882B2 (en) | ||
| EP0123385B1 (en) | Humidity-sensitive resistive element | |
| JPS6327841B2 (en) | ||
| JPH0552795A (en) | Humidity sensitive element | |
| JPS5826641B2 (en) | Temperature/humidity detection element | |
| KR840000260B1 (en) | Temperature-responsive element | |
| JPS5811082B2 (en) | Temperature and humidity detection element | |
| JP3559911B2 (en) | Thermistor | |
| JPH0572157A (en) | Humidity sensing element | |
| JP3494348B2 (en) | Humidity-sensitive resistance material and humidity sensor using the same | |
| KR100225499B1 (en) | Material of metallic oxide system thermistor using for high temperature | |
| JPS6116933B2 (en) | ||
| JPH05302908A (en) | Moisture sensitive element | |
| JPS6351363B2 (en) | ||
| JPH05142183A (en) | Moisture sensitive element | |
| JPH0237046B2 (en) | ||
| KR900003930B1 (en) | Gas detector | |
| JPH0552793A (en) | Humidity sensitive element | |
| JPS6359521B2 (en) | ||
| JPS5832401A (en) | Humidity sensitive resistor |