JPH0122965B2 - - Google Patents
Info
- Publication number
- JPH0122965B2 JPH0122965B2 JP58048515A JP4851583A JPH0122965B2 JP H0122965 B2 JPH0122965 B2 JP H0122965B2 JP 58048515 A JP58048515 A JP 58048515A JP 4851583 A JP4851583 A JP 4851583A JP H0122965 B2 JPH0122965 B2 JP H0122965B2
- Authority
- JP
- Japan
- Prior art keywords
- glass frit
- humidity
- ruthenium oxide
- amount
- humidity sensor
- 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
- 239000011521 glass Substances 0.000 claims description 20
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 13
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims description 12
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 3
- 239000007772 electrode material Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 4
- 239000011148 porous material Substances 0.000 description 3
- 229910018068 Li 2 O Inorganic materials 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- -1 Li 2 O Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N lead(II) oxide Inorganic materials [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
Landscapes
- 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】
本発明は電極材料を改良した金属酸化物を使用
した湿度センサの製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method of manufacturing a humidity sensor using an improved metal oxide electrode material.
一般に湿度センサは相対湿度の変化を電気抵抗
の変化として検出するもので、すばやい応答速度
を確保するため感湿素子自体がもつ気孔の電極に
よつてのふさがり度合を最小限にとどめ、しかも
感湿素子両面に形成する電極面の有効面積を最大
限確保することが要請されており、電極材料の選
定は湿度センサの特性上重要な要件である。 Humidity sensors generally detect changes in relative humidity as changes in electrical resistance.In order to ensure a quick response speed, humidity sensors minimize the degree of blockage of the pores of the humidity sensing element itself by the electrodes. It is required to maximize the effective area of the electrode surfaces formed on both sides of the element, and the selection of electrode materials is an important requirement in terms of the characteristics of the humidity sensor.
従来このような要請にこたえるべき電極材料と
してはAu，Pt，Agなどの貴金属材料が用いられ
ているが、これら貴金属材料は高価格のため湿度
センサとしてのコストを高くする結果になり、さ
らに加えて例えばAgを用いた場合感湿素子内部
にAgの粒が入つてしまうマイグレーシヨン現象
によつて大電流下でシヨートしてしまう問題があ
るなど実用面での欠点があつた。そのため近年酸
化ルテニウムが電極材料として注目されてきてい
る。しかして酸化ルテニウムを電極材料として用
いる場合感湿素子と密着させるためにある種のガ
ラスフリツト成分を加えなければならないと同時
に感湿素子自体がもつ気孔を電極によつてできる
かぎりふさぐことのない状態を確保するために、
酸化ルテニウムペースト中のガラスフリツト成分
および配合比率さらにガラスフリツトの酸化ルテ
ニウムに対する添加量はきわめて重要な条件であ
る。 Conventionally, noble metal materials such as Au, Pt, and Ag have been used as electrode materials to meet these demands, but these noble metal materials are expensive, resulting in an increase in the cost of the humidity sensor. For example, when Ag is used, there are practical drawbacks such as a migration phenomenon in which Ag particles get inside the moisture-sensitive element, causing it to shoot out under large currents. Therefore, in recent years, ruthenium oxide has attracted attention as an electrode material. However, when using ruthenium oxide as an electrode material, it is necessary to add a certain type of glass frit component to make it come into close contact with the humidity sensing element, and at the same time, it is necessary to ensure that the pores of the humidity sensing element itself are not blocked by the electrode as much as possible. In order to ensure
The glass frit components and blending ratio in the ruthenium oxide paste as well as the amount of glass frit added to the ruthenium oxide are extremely important conditions.
本発明は上記の点に鑑みてなされたもので、酸
化ルテニウムペーストにおけるガラスフリツト成
分および該フリツト成分の配合比率さらにガラス
フリツト成分全量の酸化ルテニウムに対する添加
量を規定することによつて信頼性に富んだ安価な
湿度センサを得ることのできる湿度センサの製造
方法を提供することを目的とするものである。 The present invention has been made in view of the above-mentioned points, and provides a highly reliable and inexpensive product by specifying the glass frit component in the ruthenium oxide paste, the blending ratio of the frit component, and the addition amount of the total amount of the glass frit component to the ruthenium oxide. It is an object of the present invention to provide a method for manufacturing a humidity sensor that allows a humidity sensor to be obtained.
以下本発明につき説明する。すなわち第１図お
よび第２図に示すように例えばZnO，Cr2O4，
Li2O，V2O5などの金属酸化物を適量秤取しこれ
をボールミルなどでよく混合し600〜900℃の温度
で焙焼し、さらにポリビニルアルコール水溶液を
バインダとして造粒し板状に成形し、ついで1000
〜1400℃の温度で１〜５時間焼結しその後研磨し
て焼結体(1)を形成する。つぎに該焼結体(1)の表裏
両面に外周円を残して酸化ルテニウム（RuO2）
にSiO2，PbO，MgO，Al2O3，ZrO2の配合比率
として重量比でSiO22.6：PbO3.4：MgO0.2：
Al2O31.0：ZrO22.8となるようにしたガラスフリ
ツト成分１〜10重量％添加し、他に溶剤および樹
脂などを混合した酸化ルテニウムペーストをスク
リーン印刷し120℃で乾燥し700〜900℃で３分間
焼付し電極２ａ，２ｂを形成し、該電極２ａ，２
ｂにそれぞれ端子３ａ，３ｂを接続してなるもの
である。 The present invention will be explained below. That is, as shown in FIGS. 1 and 2, for example, ZnO, Cr 2 O 4 ,
Weigh out appropriate amounts of metal oxides such as Li 2 O, V 2 O 5 , etc., mix well with a ball mill, etc., roast at a temperature of 600 to 900°C, and then granulate into a plate shape using an aqueous polyvinyl alcohol solution as a binder. Molded and then 1000
It is sintered at a temperature of ~1400° C. for 1 to 5 hours and then polished to form a sintered body (1). Next, ruthenium oxide (RuO 2 ) is applied to both the front and back sides of the sintered body (1), leaving an outer circumferential circle on both sides.
The blending ratio of SiO 2 , PbO, MgO, Al 2 O 3 and ZrO 2 is SiO 2 2.6:PbO3.4:MgO0.2:
A ruthenium oxide paste made by adding 1 to 10% by weight of a glass frit component with a ratio of Al 2 O 3 1.0:ZrO 2 2.8, and a mixture of solvent and resin, etc., was screen printed, dried at 120℃, and dried at 700 to 900℃. The electrodes 2a, 2b are formed by baking for 3 minutes, and the electrodes 2a, 2
Terminals 3a and 3b are connected to terminals 3a and 3b, respectively.
以上のように構成してなる湿度センサの製造方
法によれば電極材料として重要な要件である感湿
素子自体がもつ気孔のふさがり度合を最小限にと
どめ電極面の有効面積を最大限確保できるため特
性劣化がなく信頼性に富む効果を発揮する。 According to the manufacturing method of the humidity sensor configured as described above, it is possible to minimize the degree of clogging of the pores of the humidity sensing element itself, which is an important requirement for electrode materials, and to ensure the maximum effective area of the electrode surface. Demonstrates highly reliable effects with no characteristic deterioration.
つぎに実施例にもとずき本発明をさらに詳細に
説明する。まずZnO50モル％，Cr2O441モル％，
Li2O4.5モル％、V2O54.5モル％を秤取しこれをボ
ールミルでよく混合する。ついでこれらの混合物
を800℃の温度で焙焼し、しかるのちポリビニル
アルコール水溶液を添加混合し厚さ0.24mm直径９
mmの円板成形体を得る。しかして該円板成形体を
1300℃の温度で３時間焼結して得た感湿素子の表
裏両面に外周縁を残してRuO2に重量比で
SiO22.6：PbO3.4：MgO0.2：Al2O31.0：ZrO22.8
の配合比率からなるガラスフリツト成分の添加量
（重量比で）としてそれぞれ違わせた酸化ルテニ
ウムをスクリーン印刷して120℃にて乾燥し、し
かるのち800℃にて３分間焼付けを行い電極を形
成した湿度センサそれぞれのガラスフリツト添加
量に対する変化桁、ヒステリシスおよび湿度変化
率特性を測定した結果、第３図〜第８図に示すよ
うになつた。なお試料として用いたガラスフリツ
ト添加量は0.5％，１％，３％，５％，10％，15
％，20％の７種類である。 Next, the present invention will be explained in more detail based on Examples. First, ZnO 50 mol%, Cr 2 O 4 41 mol%,
Weigh out 4.5 mol % of Li 2 O and 4.5 mol % of V 2 O 5 and mix them well in a ball mill. Next, these mixtures were roasted at a temperature of 800°C, and then a polyvinyl alcohol aqueous solution was added and mixed to form a 9.5 mm thick, 0.24 mm diameter
Obtain a disc molded body of mm. However, the disc molded body
The moisture-sensitive element was sintered at a temperature of 1300°C for 3 hours, and the outer periphery was left on both the front and back sides, and RuO 2 was added in a weight ratio.
SiO 2 2.6: PbO3.4: MgO0.2: Al 2 O 3 1.0: ZrO 2 2.8
Screen-printed ruthenium oxide with different amounts (by weight) of the glass frit component in the blending ratio, dried at 120℃, and then baked at 800℃ for 3 minutes to form electrodes. The results of measuring the change digit, hysteresis, and humidity change rate characteristics with respect to the amount of glass frit added for each sensor were as shown in FIGS. 3 to 8. The amounts of glass frit added as samples were 0.5%, 1%, 3%, 5%, 10%, 15
There are seven types: %, 20%.
第３図はガラスフリツト添加量に対するR30／
R90の変化桁を示すもので、第４図はガラスフリ
ツト添加量に対する50％RHのヒステリシスを示
すもので、さらに第５図〜第８図はガラスフリツ
ト添加量に対する50℃90％RH中に5000h放置し
たときの相対湿度30％RH，50％RH，70％RH，
90％RHそれぞれの抵抗値の変化を変化率で表わ
した湿度変化率を示すものである。 Figure 3 shows R 30 /
Figure 4 shows the hysteresis of 50%RH with respect to the amount of glass frit added, and Figures 5 to 8 show the 50%RH hysteresis with respect to the amount of glass frit added. Relative humidity at 30%RH, 50%RH, 70%RH,
This shows the humidity change rate, which represents the change in resistance value at 90% RH.
第３図〜第８図から明らかなようにガラスフリ
ツト添加量として１〜10重量％のものは変化桁が
大きくヒステリシスは小さく初期特性においてす
ぐれていると同時に、高温高湿中における放置試
験においても湿度変化率は変わらず長時間安定し
た特性を維持できるすぐれた効果を実証した。 As is clear from Figures 3 to 8, when the amount of glass frit added is 1 to 10% by weight, the change is large, the hysteresis is small, and the initial characteristics are excellent. We have demonstrated the excellent effect of maintaining stable characteristics for a long time without changing the rate of change.
以上述べたように本発明によれば酸化ルテニウ
ムに配合比率として重量比でSiO22.6：PbO3.4：
MgO0.2：Al2O31.0：ZrO22.8となるようにしたガ
ラスフリツト成分を全重量に対して１〜10重量％
添加した酸化ルテニウムペーストを感湿素子表裏
両面に焼付けて電極を形成することによつて初期
特性はもとより信頼性に富んだ安価な湿度センサ
を得ることのできる湿度センサの製造方法を提供
できる。 As described above, according to the present invention, the compounding ratio of ruthenium oxide is SiO 2 2.6:PbO3.4:
The glass frit component has a composition of MgO0.2: Al 2 O 3 1.0: ZrO 2 2.8 in an amount of 1 to 10% by weight based on the total weight.
By baking the added ruthenium oxide paste on both the front and back surfaces of the humidity sensing element to form electrodes, it is possible to provide a method for manufacturing a humidity sensor that can obtain an inexpensive humidity sensor with excellent initial characteristics and high reliability.
第１図および第２図は本発明によつて得た湿度
センサの一例を示すもので第１図は平面図、第２
図は側面図、第３図はガラスフリツト添加量−変
化桁特性曲線図、第４図はガラスフリツト添加量
−ヒスリテシス特性曲線図、第５図はガラスフリ
ツト添加量−30％RHの湿度変化率特性曲線図、
第６図はガラスフリツト添加量−50％RHの湿度
変化率特性曲線図、第７図はガラスフリツト添加
量−70％RHの湿度変格率特性曲線図、第８図は
ガラスフリツト添加量−90％RHの湿度変化率特
性曲線図である。
１……感湿素子、２ａ，２ｂ……電極。
1 and 2 show an example of a humidity sensor obtained according to the present invention.
The figure is a side view, Figure 3 is a glass frit addition amount vs. variation digit characteristic curve, Figure 4 is a glass frit addition amount vs. hysteresis characteristic curve, and Figure 5 is a glass frit addition amount vs. 30% RH humidity change rate characteristic curve. ,
Figure 6 is a humidity change rate characteristic curve for glass frit addition amount - 50%RH, Figure 7 is a humidity change rate characteristic curve for glass frit addition amount - 70%RH, and Figure 8 is a humidity change rate characteristic curve for glass frit addition amount - 90%RH. It is a humidity change rate characteristic curve diagram. 1... Moisture sensing element, 2a, 2b... Electrode.
Claims (1)
PbO3.4：MgO0.2：Al2O31.0：ZrO22.8の配合比
率からなるガラスフリツト成分を全重量に対して
１〜10重量％添加した酸化ルテニウムペーストを
感湿素子表裏両面に焼付け電極を形成したことを
特徴とする湿度センサの製造方法。1 SiO 2 in weight ratio of 2.6 to ruthenium oxide:
A ruthenium oxide paste containing a glass frit component with a blending ratio of PbO3.4:MgO0.2:Al 2 O 3 1.0:ZrO 2 2.8 in an amount of 1 to 10% by weight based on the total weight is baked onto both the front and back surfaces of the moisture-sensitive element. A method for manufacturing a humidity sensor, characterized in that:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58048515A JPS59197102A (en) | 1983-03-22 | 1983-03-22 | Method of producing moisture sensor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58048515A JPS59197102A (en) | 1983-03-22 | 1983-03-22 | Method of producing moisture sensor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59197102A JPS59197102A (en) | 1984-11-08 |
| JPH0122965B2 true JPH0122965B2 (en) | 1989-04-28 |
Family
ID=12805499
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58048515A Granted JPS59197102A (en) | 1983-03-22 | 1983-03-22 | Method of producing moisture sensor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59197102A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002357581A (en) * | 2001-05-31 | 2002-12-13 | Ngk Spark Plug Co Ltd | Humidity sensor |
-
1983
- 1983-03-22 JP JP58048515A patent/JPS59197102A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002357581A (en) * | 2001-05-31 | 2002-12-13 | Ngk Spark Plug Co Ltd | Humidity sensor |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59197102A (en) | 1984-11-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4464647A (en) | Humidity sensor made of metal oxide | |
| JPH0122965B2 (en) | ||
| JPH0378761B2 (en) | ||
| JPH027162B2 (en) | ||
| JPS6327841B2 (en) | ||
| JPH0122964B2 (en) | ||
| JPS6145180B2 (en) | ||
| JPS6145181B2 (en) | ||
| JPS5813003B2 (en) | Kanshitsusoshi | |
| JPS6317203B2 (en) | ||
| JPS5811721B2 (en) | Kanshitsusoshi | |
| JPS6250778B2 (en) | ||
| JPS6317205B2 (en) | ||
| JPH058841B2 (en) | ||
| JPH058561B2 (en) | ||
| JPS5813002B2 (en) | Kanshitsusoshi | |
| JPS6317209B2 (en) | ||
| JPS6161241B2 (en) | ||
| JPS6317206B2 (en) | ||
| JPS6317207B2 (en) | ||
| JPH0465521B2 (en) | ||
| JPS6351363B2 (en) | ||
| JPS6024565B2 (en) | moisture sensing element | |
| JPS6317204B2 (en) | ||
| JPS6317208B2 (en) |