JPS6359983B2 - - Google Patents
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- Publication number
- JPS6359983B2 JPS6359983B2 JP56066638A JP6663881A JPS6359983B2 JP S6359983 B2 JPS6359983 B2 JP S6359983B2 JP 56066638 A JP56066638 A JP 56066638A JP 6663881 A JP6663881 A JP 6663881A JP S6359983 B2 JPS6359983 B2 JP S6359983B2
- Authority
- JP
- Japan
- Prior art keywords
- humidity
- resistance
- sensing element
- moisture
- electrode
- 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
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- 239000000203 mixture Substances 0.000 claims description 18
- 239000000919 ceramic Substances 0.000 claims description 9
- 229910006854 SnOx Inorganic materials 0.000 claims description 4
- 229910003087 TiOx Inorganic materials 0.000 claims description 4
- HLLICFJUWSZHRJ-UHFFFAOYSA-N tioxidazole Chemical group CCCOC1=CC=C2N=C(NC(=O)OC)SC2=C1 HLLICFJUWSZHRJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 3
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 3
- 230000006835 compression Effects 0.000 claims 1
- 238000007906 compression Methods 0.000 claims 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 14
- 238000005259 measurement Methods 0.000 description 8
- 229910010413 TiO 2 Inorganic materials 0.000 description 7
- 229910052697 platinum Inorganic materials 0.000 description 7
- 229910006404 SnO 2 Inorganic materials 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 230000032683 aging Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 101100257812 Caenorhabditis elegans ssp-10 gene Proteins 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
- Non-Adjustable Resistors (AREA)
Description
【発明の詳細な説明】
本発明は、複合酸化物半導体の焼結体からなる
感湿抵抗体磁器組成物に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a moisture-sensitive resistor ceramic composition comprising a sintered body of a composite oxide semiconductor.
湿度によつて電気抵抗が変化する性質を利用し
て感湿素子として用いられる感湿抵抗体として
は、従来よりFe2O3，Fe3O4，TiO2，ZnO，
Al2O3等の金属酸化物が知られている。これらの
金属酸化物は、化学的および熱的に安定な性質を
有するが、固有抵抗が比較的高く、またヒステリ
シス特性を有すると共に湿分の吸脱着の繰り返し
により吸湿特性が経時的に劣化する等の問題を有
している。 Humidity-sensitive resistors, which are used as humidity-sensing elements by taking advantage of the property that electrical resistance changes depending on humidity, have traditionally been made of Fe 2 O 3 , Fe 3 O 4 , TiO 2 , ZnO,
Metal oxides such as Al 2 O 3 are known. Although these metal oxides have chemically and thermally stable properties, they have relatively high specific resistance and hysteresis characteristics, and their hygroscopic properties deteriorate over time due to repeated absorption and desorption of moisture. I have this problem.
また、比較的低い固有抵抗を有する感湿素子と
してサーミスタと呼ばれる酸化物半導体がある
が、これは周知の通り大きな負の抵抗温度係数を
有しているために、温度変化を伴う条件下では湿
度測定が困難であるという問題があつた。 In addition, there is an oxide semiconductor called a thermistor as a humidity sensing element with a relatively low resistivity, but as is well known, this has a large negative temperature coefficient of resistance, so under conditions of temperature changes There was a problem that measurement was difficult.
本発明は、このような従来技術の問題を解決す
るためになされたものであり、その目的は、温度
に影響されずかつ広範囲で安定な湿度−抵抗特性
が得られる感湿抵抗体磁器組成物を提供すること
にある。 The present invention was made to solve the problems of the prior art, and its purpose is to provide a moisture-sensitive resistor ceramic composition that is not affected by temperature and has stable humidity-resistance characteristics over a wide range. Our goal is to provide the following.
このような目的を達成するために、本発明によ
る感湿抵抗体磁器組成物は、SnOx（１＜ｘ≦２）
１〜99モル％およびTiOx（１＜ｘ≦２）99〜１
モル％を主成分とし、これにTa2O5，Sb2O5，
Nb2O5，WO3，In2O3，MoO3，SiO2，ランタン
系希土類酸化物の少なくとも１種を添加し、これ
を圧縮成型した後、加熱焼成したものである。以
下、実施例を用いて本発明による感湿抵抗体磁器
組成物を詳細に説明する。 In order to achieve this purpose, the moisture-sensitive resistor ceramic composition according to the present invention contains SnOx (1<x≦2)
1 to 99 mol% and TiOx (1<x≦2)99 to 1
The main components are Ta 2 O 5 , Sb 2 O 5 ,
At least one of Nb 2 O 5 , WO 3 , In 2 O 3 , MoO 3 , SiO 2 , and lanthanum-based rare earth oxides was added, and this was compressed and then heated and fired. EXAMPLES Hereinafter, the moisture-sensitive resistor ceramic composition according to the present invention will be explained in detail using Examples.
先ず、主成分としてTiO2とSnO2とを用い、こ
れらをモル比で１：１の割合で精秤して混合す
る。この場合、実際上TiO2，SnO2中にはそれぞ
れTiO，SnOが混入しているため、全体として当
該混合物の組成はTiOx，SnOx（１＜ｘ≦２）と
なる。次に、この主成分に添加物としてTa2O5を
3.85wt％混入し、メノウ擂潰機を用いて乾式混合
を行なう。次いでこの混合粉末を島津製作所のハ
ンドプレスSSP−10型を用いて80Kgｆ／cm2の圧力
で圧縮して直径８mmφ、厚み１mmのタブレツト状
に成型した後、引き続きアルミボートに載せてシ
リコニツト発熱体を用いた電気炉に入れ、空気中
で1250℃、２時間の焼成を行なう。なお、上記80
Kgｆ／cm2のプレス圧力はメータ上の読取値であ
り、この場合、実際に試料にかかる圧力は、金型
の直径が８mmφであるのに対してラムの直径が
42.6mmφであるところから、ほぼ2300Kg／cm2であ
る。 First, using TiO 2 and SnO 2 as the main components, they are accurately weighed and mixed at a molar ratio of 1:1. In this case, since TiO 2 and SnO 2 actually contain TiO and SnO, respectively, the overall composition of the mixture is TiOx and SnOx (1<x≦2). Next, Ta 2 O 5 is added to this main component as an additive.
Mix 3.85wt% and perform dry mixing using an agate crusher. Next, this mixed powder was compressed at a pressure of 80 Kgf/cm 2 using a Shimadzu hand press SSP-10 model to form a tablet with a diameter of 8 mmφ and a thickness of 1 mm.Then, the tablet was placed on an aluminum boat and a silicone heating element was placed on it. The product was placed in the same electric furnace and fired in air at 1250°C for 2 hours. In addition, above 80
The press pressure of Kgf/cm 2 is the reading on the meter, and in this case, the actual pressure applied to the sample is 8 mmφ in diameter while the diameter of the ram is 8 mmφ.
Since it is 42.6mmφ, it is approximately 2300Kg/cm 2 .
このようにして形成した感湿抵抗体磁器組成物
を厚み0.4mmにまで研磨し、出来上がつた感湿体
を用いて第１図に示すような感湿素子１を形成す
る。同図ａはその正面図、同図ｂはその平面図を
示す。即ち、当該感湿体２の１主面上に白金電極
３、他主面上にRuO2電極４が設けてある。この
RuO2電極４は、白金電極３の対向電極であると
共に、後述するようにクリーニング用の加熱電極
を兼ねており、両端部に銀ペースト５を塗布して
そこからリード線６ａを引き出してある。前記白
金電極３の中央部からもリード線６ｂが引き出し
てある。これらのリード線６ａ，６ｂは、各電極
と外部との電気的接続をはかると共に、感湿体２
をマウントステム７に保持する支持体の機能を果
している。なお、白金電極３およぢRuO2電極４
は、それぞれ白金ペーストおよびRuO2ペースト
をスクリーン印刷することによつて形成する。 The humidity-sensitive resistor ceramic composition thus formed was polished to a thickness of 0.4 mm, and the resulting humidity-sensitive resistor was used to form a humidity-sensitive element 1 as shown in FIG. Figure a shows its front view, and figure b shows its plan view. That is, a platinum electrode 3 is provided on one main surface of the moisture sensitive body 2, and a RuO 2 electrode 4 is provided on the other main surface. this
The RuO 2 electrode 4 is a counter electrode to the platinum electrode 3, and also serves as a heating electrode for cleaning as will be described later.A silver paste 5 is applied to both ends of the RuO 2 electrode 4, from which a lead wire 6a is drawn out. A lead wire 6b is also drawn out from the center of the platinum electrode 3. These lead wires 6a, 6b provide electrical connection between each electrode and the outside, and also connect the moisture sensitive element 2.
It functions as a support for holding the mount stem 7 on the mount stem 7. In addition, platinum electrode 3 and RuO 2 electrode 4
are formed by screen printing platinum paste and RuO 2 paste, respectively.
この感湿素子を恒温槽に入れ、雰囲気の相対湿
度を変えて電極間の抵抗値を測定することによ
り、第２図に示すような湿度−抵抗特性が得られ
た。同図においてイ，ロ，ハはそれぞれ温度が30
℃、40℃、50℃のときの特性を示す。なおこの場
合、素子の抵抗が比較的高いため、測定回路とし
ては60Hz、1Vの電源に素子と10KΩの抵抗を直
列に接続した回路を用い、この抵抗の両端の電圧
を測定し、その値を用いて素子の抵抗値を算出し
た。 The humidity-resistance characteristic shown in FIG. 2 was obtained by placing this humidity-sensitive element in a constant temperature bath and measuring the resistance value between the electrodes while changing the relative humidity of the atmosphere. In the same figure, A, B, and C each have a temperature of 30
Characteristics at ℃, 40℃, and 50℃ are shown. In this case, since the resistance of the element is relatively high, the measurement circuit is a circuit that connects the element and a 10KΩ resistor in series to a 60Hz, 1V power supply, measures the voltage across this resistor, and calculates the value. The resistance value of the element was calculated using
同図から明らかなように、相対湿度が20〜90％
の広い範囲にわたつて殆んど直線的な特性が得ら
れる。また、温度による影響も極めて少ないこと
が分る。 As is clear from the figure, the relative humidity is between 20 and 90%.
Almost linear characteristics are obtained over a wide range of . It can also be seen that the influence of temperature is extremely small.
なお、第３図に、相対湿度に対するこの感湿素
子の等価並列抵抗イおよび等価並列容量ロを示
す。同図は、100Hzの電源を用い、40℃の温度下
で測定した場合の特性であるが、同図より、相対
湿度の変化に対して容量値の変化の方が抵抗値の
変化に比較して著しく小さいことが分る。 Incidentally, FIG. 3 shows the equivalent parallel resistance (a) and equivalent parallel capacitance (b) of this humidity sensing element with respect to relative humidity. The figure shows the characteristics when measured at a temperature of 40℃ using a 100Hz power supply, but from the figure it can be seen that the change in capacitance value is greater than the change in resistance value with respect to changes in relative humidity. It can be seen that it is significantly smaller.
第４図は、上記感湿素子の湿度応答特性を示す
図である。即ち同図イおよびロは、それぞれ相対
湿度を60％から95％に増加したときおよび95％か
ら60％に減少したときの平衡時間を示す。なお、
同図は30℃の温度下で測定したものである。同図
から明らかなようにイの吸湿の場合、およびロの
脱湿の場合のいずれも約10秒間で平衡し、従来の
薄膜型の感湿素子に比較して早い吸脱湿平衡時間
を示す素子が得られることが分る。 FIG. 4 is a diagram showing the humidity response characteristics of the humidity sensitive element. That is, A and B in the figure show the equilibrium time when the relative humidity is increased from 60% to 95% and when it is decreased from 95% to 60%, respectively. In addition,
The figure was measured at a temperature of 30°C. As is clear from the figure, equilibrium takes about 10 seconds for both moisture absorption (a) and moisture removal (b), indicating a faster moisture absorption and desorption equilibrium time compared to conventional thin-film moisture sensing elements. It can be seen that a device can be obtained.
更に、上記感湿素子に100Hz，1Vの電圧を印加
し、40℃、85％RHの雰囲気中に2400時間放置し
たところ、、湿度−抵抗特性は約80時間で平衡に
至り、その後の経時変化は数％以内であつた。こ
の様子を第５図、第６図に示す。第５図は時間と
抵抗との関係を示したものであり、抵抗は初期値
R0に対する比で示してある。なお、抵抗の測定
は30℃、60％RHの条件下で、第２図について説
明したと同様に10KΩの抵抗を直列接続し、60
Hz，1Vの電源を用いて行なつた。また、第６図
は時間をパラメータとして湿度−抵抗特性を示し
たものであり、同図中実線イは製造直後の特性を
示す。また実線ロは製造後28日で経時試験を開始
する直前の特性、破線ハは1000時間後、ニは2400
時間後の特性を示す。なお、測定はいずれも30℃
の温度下で10KΩの抵抗を直列し、1Vの交流電
源を用いて行なつた。 Furthermore, when a voltage of 100 Hz and 1 V was applied to the above humidity sensing element and it was left in an atmosphere of 40°C and 85% RH for 2400 hours, the humidity-resistance characteristics reached equilibrium in about 80 hours, and the subsequent changes over time were observed. was within a few percent. This situation is shown in FIGS. 5 and 6. Figure 5 shows the relationship between time and resistance, where resistance is the initial value.
It is expressed as a ratio to R 0 . The resistance was measured under the conditions of 30℃ and 60%RH by connecting 10KΩ resistors in series as explained in Figure 2.
This was done using a Hz, 1V power supply. Further, FIG. 6 shows the humidity-resistance characteristics using time as a parameter, and the solid line A in the figure shows the characteristics immediately after manufacture. In addition, the solid line B shows the characteristics immediately before starting the aging test 28 days after manufacturing, the broken line C shows the characteristics after 1000 hours, and the D shows the characteristics after 2400 hours.
Characteristics after time are shown. All measurements were taken at 30℃.
The experiment was carried out using a 1V AC power supply with a 10KΩ resistor connected in series at a temperature of .
第５図、第６図から明らかなように、前記感湿
素子は極めて安定な経時特性を有し、通常の使用
環境においては、加熱再生をしなくても素子の特
性は劣化しない。 As is clear from FIGS. 5 and 6, the moisture-sensitive element has extremely stable characteristics over time, and in a normal usage environment, the characteristics of the element do not deteriorate even without heat regeneration.
第７図に、上述した本発明による感湿抵抗体磁
器組成物からなる感湿素子１を用いて相対湿度を
測定するための測定回路の一例を示す。同図にお
いて、交流電源８に、スイツチ９、抵抗Rsおよ
び感湿素子１が直列に接続してある。抵抗Rsに
は該抵抗Rsの端子電圧を増幅する対数変換増幅
器１０が並列に接続してあり、この対数変換増幅
器１０の出力が指示制御回路１１の入力となる。
また、感湿体２の１主面に設けたRuO2電極４の
両端は、スイツチ１２を介して交流電極１３に接
続してある。スイツチ１２はタイマ１４の出力に
よつて動作するリレー１５によつて開閉し、かつ
前記スイツチ９と連動しており、一方がオンの時
他方はオフの関係にある。 FIG. 7 shows an example of a measuring circuit for measuring relative humidity using the humidity sensing element 1 made of the above-mentioned humidity-sensitive resistor ceramic composition according to the present invention. In the figure, a switch 9, a resistor Rs, and a humidity sensing element 1 are connected in series to an AC power source 8. A logarithmic conversion amplifier 10 for amplifying the terminal voltage of the resistor Rs is connected in parallel to the resistor Rs, and the output of this logarithmic conversion amplifier 10 becomes the input of the instruction control circuit 11.
Further, both ends of the RuO 2 electrode 4 provided on one main surface of the moisture sensitive body 2 are connected to an AC electrode 13 via a switch 12 . The switch 12 is opened and closed by a relay 15 operated by the output of the timer 14, and is interlocked with the switch 9, so that when one is on, the other is off.
上記構成を有する測定回路において、スイツチ
９がオン、スイツチ１２がオフの状態で、感湿素
子１、交流電源８、抵抗Rsからなる閉開路が形
成され、感湿素子１の抵抗の変化は抵抗Rsの端
子電圧の変化として現われる。従つて、指示制御
回路１１によつて湿度が表示され、正常な湿度測
定ができる。 In the measurement circuit having the above configuration, when the switch 9 is on and the switch 12 is off, a closed/open circuit consisting of the humidity sensing element 1, the AC power supply 8, and the resistor Rs is formed, and the change in the resistance of the humidity sensing element 1 is caused by the resistance. It appears as a change in the terminal voltage of Rs. Therefore, the humidity is displayed by the instruction control circuit 11, and normal humidity measurement can be performed.
この場合、前述したように通常の環境において
は素子の特性は殆んど劣化することはないが、例
えば油や塵埃等による汚染が特に著しい悪環境に
おいて使用する場合には、素子を加熱して汚染物
質を焼き飛ばし、再生することが必要となる場合
がある。前述したように感湿素子１のRuO2の電
極４はこのためのヒータを兼ねており、第７図に
おいてスイツチ９がオフ、スイツチ１２がオンの
状態で、交流電源１３によりRuO2電極４の両端
に電力が供給され、該RuO2電極４に流れる電流
により感湿素子１は加熱され回復する。この場
合、加熱温度が450℃程度になるように交流電源
１３の電圧を設定しておく。一定時間（例えば５
分間）の後、再びスイツチ９をオン、スイツチ１
２をオフとして正常の湿度測定が行なわれる。ス
イツチ９および１２の反転は、前述したようにタ
イマ１４の出力によつて動作するリレー１５によ
つて連動して行なわれ、自動的に一定時間毎の回
復作業を繰り返しながら湿度測定が続けられる。 In this case, as mentioned above, the characteristics of the element will hardly deteriorate in a normal environment, but if the element is used in a particularly bad environment where contamination with oil or dust is particularly severe, the element may be heated. It may be necessary to burn off contaminants and regenerate. As mentioned above, the RuO 2 electrode 4 of the humidity sensing element 1 also serves as a heater for this purpose, and in FIG. 7, when the switch 9 is off and the switch 12 is on, the RuO 2 electrode 4 is Electric power is supplied to both ends, and the current flowing through the RuO 2 electrode 4 heats the humidity sensing element 1 and restores it. In this case, the voltage of the AC power supply 13 is set so that the heating temperature is about 450°C. A certain period of time (for example, 5
), turn switch 9 on again, switch 1
2 is turned off and normal humidity measurement is performed. The reversal of the switches 9 and 12 is carried out in conjunction with the relay 15 operated by the output of the timer 14 as described above, and humidity measurement is continued while automatically repeating the recovery operation at fixed time intervals.
第８図はSnO2，TiO2系混合体のみにより形成
された感湿素子およびSnO2，TiO2系混合体に添
加物としてTa2O5を5wt％添加して形成された感
湿素子の湿度対抵抗特性をそれぞれ比較して示し
たものである。同図に曲線Ａで示すようにSn，
Ti系混合体のみによる感湿素子は、同図に曲線
Ｂで示すTa2O5を添加した感湿素子に比べて湿度
対抵抗特性が極めて悪い。これに対してTa2O5を
添加した感湿素子は曲線Ｂで示すように、広い相
対湿度範囲にわたつてほぼ直線的な特性が得られ
た。 Figure 8 shows a humidity sensing element formed only from a SnO 2 and TiO 2 mixture and a moisture sensing element formed by adding 5 wt% of Ta 2 O 5 as an additive to the SnO 2 and TiO 2 mixture. This shows a comparison of the humidity vs. resistance characteristics. As shown by curve A in the figure, Sn,
A humidity sensing element made only of a Ti-based mixture has extremely poor humidity resistance characteristics compared to a humidity sensing element added with Ta 2 O 5 shown by curve B in the figure. On the other hand, as shown by curve B, the humidity sensitive element containing Ta 2 O 5 had substantially linear characteristics over a wide range of relative humidity.
これはSnO2，TiO2系混合体に第３の成分とし
てTa2O5，Sb2O5等を添加することにより、４価
の原子であるSn，Tiに対して５価であるTa，Sb
等が添加されることであり、これによつて原子価
制御によるキヤリア濃度が増加し、感湿時におけ
る電気伝導度を大きく変化させる機能を有してお
り、結果として第８図に曲線Ｂで示すように、低
インピーダンス化された感湿素子が得られること
になる。したがつて検出信号が取扱易くなる。 By adding Ta 2 O 5 , Sb 2 O 5 , etc. as the third component to the SnO 2 , TiO 2 -based mixture, the pentavalent Ta, Sb
This increases the carrier concentration through valence control and has the function of greatly changing the electrical conductivity during humidity sensing, resulting in the curve B shown in Figure 8. As shown, a moisture sensitive element with low impedance is obtained. Therefore, the detection signal becomes easier to handle.
なお、上述した実施例においては、主成分とし
てのSnOxとTiOx（１＜ｘ≦２）とを１：１の割
合で混合した場合についてのみ説明したが、本発
明はこれに限定されるものではなく、他の割合で
も同様の特性が得られる。但し、一方が１モル％
未満になつた場合には所望の特性が得られなくな
るため、それぞれ１〜99モル％である必要があ
る。 In addition, in the above-mentioned example, only the case where SnOx and TiOx (1<x≦2) as main components were mixed at a ratio of 1:1 was explained, but the present invention is not limited to this. Similar characteristics can be obtained with other ratios. However, one side is 1 mol%
If the content is less than that, the desired properties cannot be obtained, so the content needs to be 1 to 99 mol%.
また、添加物としては、上述したTa2O5の外、
NaH2PO42H2OSb2O5，Nb2O5，WO3，In2O3，
M0O3，SiO2，ランタン系希土類酸化物等でもよ
く、これらは、いずれか１種を用いてもよいし、
いくつか組合せて用いてもよい。また添加量は、
２〜15wt％の範囲内であれば満足する特性が得
られる。 In addition, as additives, in addition to the above-mentioned Ta 2 O 5 ,
NaH 2 PO 4 2H 2 OSb 2 O 5 , Nb 2 O 5 , WO 3 , In 2 O 3 ,
M 0 O 3 , SiO 2 , lanthanum-based rare earth oxides, etc. may be used, and any one of these may be used, or
Some may be used in combination. Also, the amount added is
Satisfactory properties can be obtained within the range of 2 to 15 wt%.
すなわち、SnO2，TiO2系混合体を構成する
Sn，Tiは４価の原子から成り、添加物のTa2O5，
Sb2O5，Nb2O5等を構成するそれぞれTa，Sb，
Nbは５価の原子から成つており、この原子価の
差により原子価制御によるキヤリア濃度が増加
し、電気伝導度の変化が大きくなることから、４
価の原子から成る金属を除く３価、５価もしくは
６価の原子から成る金属酸化物を添加することに
より、ほぼ同等の作用効果が得られる。 In other words, it constitutes a SnO 2 , TiO 2 based mixture.
Sn and Ti consist of tetravalent atoms, and the additives Ta 2 O 5 ,
Ta, Sb, etc., which constitute Sb 2 O 5 , Nb 2 O 5 , etc.
Nb is composed of pentavalent atoms, and this difference in valence increases the carrier concentration due to valence control, which increases the change in electrical conductivity.
By adding a metal oxide consisting of trivalent, pentavalent or hexavalent atoms, excluding metals consisting of valent atoms, substantially the same effect can be obtained.
また、添加物の添加量については、その量が
2wt％未満になると、添加滅を全く加えない場合
とほぼ同等の特性（第８図の曲線Ａ）となり、ま
たその量が15wt％を越えると広い範囲で直線性
を有する安定な特性（第８図の曲線Ｂ）が得られ
なくなるとともに、製造コストが増大することに
なる。したがつて添加量は２〜15wt％の範囲と
することにより、第８図の曲線Ｂの上下方向にあ
る一定の幅を有する直線性の特性が得られるとと
もに、第８図の曲線Ａに比べて抵抗値が低い、つ
まり低インピーダンスの感湿素子が得られること
になる。 Also, regarding the amount of additives added, the amount
When the amount is less than 2wt%, the characteristics are almost the same as when no additive is added at all (curve A in Figure 8), and when the amount exceeds 15wt%, the characteristics are stable with linearity over a wide range (curve 8). Curve B) in the figure cannot be obtained, and manufacturing costs will increase. Therefore, by setting the amount added in the range of 2 to 15 wt%, linearity characteristics with a certain width in the vertical direction of curve B in Fig. 8 can be obtained, and compared to curve A in Fig. 8, linearity characteristics can be obtained. Therefore, a moisture sensing element with a low resistance value, that is, a low impedance can be obtained.
更に、上述した実施例においては、圧縮成型時
のプレス圧力が80Kg／cm2であり、かつ焼結条件が
1250℃、２時間である場合について説明したが、
このプレス条件と焼結条件との組合せは、製造さ
れる素子の経時特性と回復特性とに大きく影響
し、それぞれ30〜20Kgｆ／cm2（メータ値）、即ち
実際に試料に加わる圧力としてほぼ850〜5700
Kg／cm2および1100〜1400℃、30分〜３時間の範囲
内であれば良好な特性を得ることができる。 Furthermore, in the above-mentioned example, the press pressure during compression molding was 80Kg/ cm2 , and the sintering conditions were
I explained the case of 1250℃ for 2 hours,
The combination of these pressing conditions and sintering conditions greatly influences the aging characteristics and recovery characteristics of the manufactured device, and each is 30 to 20 Kgf/cm 2 (meter value), that is, approximately 850 kgf/cm 2 (meter value) as the pressure actually applied to the sample. ~5700
Good properties can be obtained within the range of Kg/cm 2 and 1100 to 1400°C for 30 minutes to 3 hours.
なお、上述した実施例においては加熱再生用の
ヒータとして、白金電極３の対向電極としての
RuO2電極４を兼用したが、これは、感湿素子１
の近傍に別個に設けてもよいことは勿論である。 In addition, in the above-mentioned embodiment, as a heater for heating and regeneration, a counter electrode of the platinum electrode 3 is used.
RuO 2 electrode 4 was also used, but this was used for humidity sensing element 1
Of course, it may be provided separately near the .
以上説明したように、本発明による感湿抵抗体
磁器組成物によれば、温度に影響されず、かつ広
い範囲で直線性を有する安定な湿度−抵抗特性を
示すと共に湿度応答特性も良好な感湿素子を得る
ことが可能となる。また、加熱装置を付加するこ
とにより、油、塵埃等の悪環境による経時変化も
容易に解消して安定した湿度測定が行なえる等の
種々優れた効果を有する。 As explained above, the humidity-sensitive resistor ceramic composition according to the present invention exhibits stable humidity-resistance characteristics that are not affected by temperature and have linearity over a wide range, and also has good humidity response characteristics. It becomes possible to obtain a wet element. Furthermore, by adding a heating device, it has various excellent effects such as easily eliminating changes over time due to adverse environments such as oil and dust, and making it possible to perform stable humidity measurements.
第１図ａおよびｂは本発明による感湿抵抗体磁
器組成物の一実施例を用いた感湿素子を示す正面
図および平面図、第２図は第１図感湿素子の湿度
−抵抗特性図、第３図は第１図の感湿素子の等価
並列抵抗および等価並列容量と相対湿度との関係
を示す特性図、第４図は第１図の感湿素子の湿度
応答特性図、第５図および第６図は第１図の感湿
素子の湿度−抵抗特性の経時変化を示す特性図、
第７図は第１図の感湿素子を用いた湿度測定回路
の一例を示す回路図、第８図はSnO2，TiO2系混
合体およびSnO2，TiO2系混合体にTa2O5を添加
して形成された感湿素子の湿度対抵抗特性を示す
図である。
１……感湿素子、２……感湿体、３……白金電
極、４……RuO2電極。
Figures 1a and b are a front view and a plan view showing a humidity sensing element using an example of the humidity sensitive resistor ceramic composition according to the present invention, and Figure 2 is the humidity-resistance characteristic of the humidity sensing element shown in Figure 1. Figure 3 is a characteristic diagram showing the relationship between the equivalent parallel resistance and equivalent parallel capacitance of the humidity sensing element in Figure 1 and relative humidity, Figure 4 is a humidity response characteristic diagram of the humidity sensing element in Figure 1, 5 and 6 are characteristic diagrams showing changes over time in the humidity-resistance characteristics of the humidity sensing element shown in FIG.
FIG . 7 is a circuit diagram showing an example of a humidity measuring circuit using the humidity sensing element of FIG . FIG. 3 is a diagram showing the humidity versus resistance characteristics of a humidity-sensitive element formed by adding . 1...Moisture sensing element, 2...Moisture sensing body, 3...Platinum electrode, 4...RuO 2 electrode.
Claims (1)
TiOx（１＜ｘ≦２）99〜１モル％を主成分とし、
かつTa2O5，Sb2O5，Nb2O5，WO3，In2O3，
MoO3，SiO2ランタン系希土類酸化物のうちの少
なくとも１種を２〜15wt％添加した混合物を圧
縮成型および加熱焼結したことを特徴とする感湿
抵抗体磁器組成物。1 SnOx (1<x≦2) 1 to 99 mol% and
The main component is TiOx (1<x≦2) 99 to 1 mol%,
and Ta 2 O 5 , Sb 2 O 5 , Nb 2 O 5 , WO 3 , In 2 O 3 ,
A moisture-sensitive resistor ceramic composition characterized in that a mixture containing 2 to 15 wt % of at least one of MoO 3 and SiO 2 lanthanum-based rare earth oxides is compression molded and heated and sintered.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56066638A JPS57183357A (en) | 1981-05-01 | 1981-05-01 | Moisture-resistant resistor ceramic composition and manufacture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56066638A JPS57183357A (en) | 1981-05-01 | 1981-05-01 | Moisture-resistant resistor ceramic composition and manufacture |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57183357A JPS57183357A (en) | 1982-11-11 |
| JPS6359983B2 true JPS6359983B2 (en) | 1988-11-22 |
Family
ID=13321635
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56066638A Granted JPS57183357A (en) | 1981-05-01 | 1981-05-01 | Moisture-resistant resistor ceramic composition and manufacture |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57183357A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4836711B2 (en) * | 2006-08-23 | 2011-12-14 | 瀬戸山家具株式会社 | Storage furniture |
-
1981
- 1981-05-01 JP JP56066638A patent/JPS57183357A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57183357A (en) | 1982-11-11 |
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