JPS5815069A - Ceramic composition for heating body - Google Patents
Ceramic composition for heating bodyInfo
- Publication number
- JPS5815069A JPS5815069A JP56112495A JP11249581A JPS5815069A JP S5815069 A JPS5815069 A JP S5815069A JP 56112495 A JP56112495 A JP 56112495A JP 11249581 A JP11249581 A JP 11249581A JP S5815069 A JPS5815069 A JP S5815069A
- Authority
- JP
- Japan
- Prior art keywords
- resistance
- heating element
- ceramic composition
- room temperature
- temperature
- 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.)
- Pending
Links
Landscapes
- Resistance Heating (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
本発明は電気抵抗の温度係数が小さい発熱体用のセラミ
ック組成物に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a ceramic composition for a heating element having a small temperature coefficient of electrical resistance.
従来より発熱体として用いられている代表的なものに、
ニッケルークロムや鉄−クロムなどの合金系発熱体、Ｓ
ｉＣやＬ ａ Ｃｒ Ｏａ ｒ Ｂ ａ Ｔ ｔ Ｏ３
などのセラミック系発熱体がある。合金系発熱体は室温
から１ｏｏＯ°Ｃに昇温してもその電気抵抗は１０〜２
０チ程度しか変化せず、また優れた耐久性もあり、広く
一般に用いられている。しかし、これらの合金はその固
有抵抗が１００ｍと低いため１、実際の使用に際しては
合金線をコイル状に巻き、耐火物の溝や石英ガラス管内
に挿入したり、絶縁碍子で保持したシする必要があるの
で、発熱体形状が制限される。一方、セラミックス系の
発熱体であるＳｉＣ，ＬａＣｒ０ やＢ ａ Ｔ １
０３などからなる３、７
ものは、薗有抵抗が合金系のものに比して高いので、要
求される抵抗値を得るために、合金系のように細い線に
してコイルに巻く必要がない。また、その形状も棒状、
螺旋状、ハニカム状と任意の形状にすることができると
いう利点を有している。Typical heating elements traditionally used include:
Alloy heating elements such as nickel-chromium and iron-chromium, S
iC and L a Cr Oa r B a T t O3
There are ceramic heating elements such as. The electrical resistance of the alloy heating element is 10 to 2 even when the temperature is raised from room temperature to 100°C.
It is widely used because it changes by only about 0 degrees and has excellent durability. However, these alloys have a low resistivity of 100 m, so in actual use, it is necessary to wind the alloy wire into a coil and insert it into a refractory groove or quartz glass tube, or to hold it with an insulator. Therefore, the shape of the heating element is limited. On the other hand, ceramic heating elements such as SiC, LaCr0 and B a T 1
3 and 7, which are made of materials such as 03, have a higher resistance than alloy-based wires, so there is no need to wind them into a thin wire like alloy-based wires in order to obtain the required resistance value. . Also, its shape is rod-like,
It has the advantage that it can be formed into any desired shape, such as a spiral or honeycomb shape.
ところが、セラミックス系の発熱体では次に述べるよう
な問題点があるので、合金系発熱体はど広く一般に用い
られることがなかった。すなわち、セラミックス系の発
熱体のうち、ＳｉＣとＬ ａＣｒ Ｏ３からなる発熱体
はそれぞれ１５００″Ｃ，１８００°Ｃまで使用可能で
あシ、工業用電気炉等に使用されているが、これらは電
気抵抗の温度変化が大きく、１０００°Ｃでは室温の抵
抗値の％−九倍となる。このため、ＳｉＣやＬ ａ Ｃ
ｒ Ｏ３を発熱体に用いる場合には発熱体の温度により
電流が大きく変化する。However, since ceramic heating elements have the following problems, alloy heating elements have not been widely used. In other words, among ceramic heating elements, heating elements made of SiC and LaCrO3 can be used up to 1500"C and 1800°C, respectively, and are used in industrial electric furnaces, etc., but these The temperature change in resistance is large, and at 1000°C it is %-9 times the resistance value at room temperature.For this reason, SiC and LaC
When rO3 is used as a heating element, the current changes greatly depending on the temperature of the heating element.
またＢ ａ Ｔ ｓ Ｏｓ系セラミックスでは、３６０
°Ｃ以下の温度で抵抗値が急激に立ち上がる現象を利用
して、定温発熱体が実用化されているが、３５０ ’Ｃ
以上では高抵抗であるため、１０００°Ｃまで使用し得
る発熱体にはならない。In addition, in B a T s Os ceramics, 360
Constant-temperature heating elements have been put into practical use by exploiting the phenomenon in which the resistance value rises rapidly at temperatures below °C;
Since the resistance is higher than that, the heating element cannot be used up to 1000°C.
室温の抵抗値ＲＲＴと１０００°Ｃの抵抗値Ｒ１ｏｏ０
の比Ｒ１０００／ＲＲＴをαとしたとき、ＳｉＣ発熱体
ではａが０．２であり、抵抗変化が大きい。前述の抵抗
比αはｏ、３≦ａ≦２の範囲にあることが望ましい。Resistance value RRT at room temperature and resistance value R1oo0 at 1000°C
When the ratio R1000/RRT is set to α, in the SiC heating element, a is 0.2, and the resistance change is large. The aforementioned resistance ratio α is desirably in the range o, 3≦a≦2.
本発明は、セラミック質の特徴である任意の形状に成型
できる利点とあわせて電気抵抗の温度変化が小さい、す
なわち上記の抵抗値比ａが０．３≦ａ≦２であり、かつ
１０００°Ｃまで使用可能な発熱体用のセラミック組成
を提供するものである。The present invention has the advantage of being able to be molded into any shape, which is a characteristic of ceramic materials, and has a small temperature change in electrical resistance, that is, the above resistance value ratio a is 0.3≦a≦2, and at 1000°C The present invention provides a ceramic composition for a heating element that can be used up to
発明者らは種々の組成のセラミックスを合成し、その電
気抵抗の温度変化を室温から１０００″Ｃで測定すると
ともに、高温度下における電気抵抗の経時変化やセラミ
ックスの耐熱衝撃性をも検討し、Ｌａ１−！ＳｒｘＭｎ
０３系のセラミックスで、０．１６≦Ｘ≦０．８の範囲
の組成物が、発熱体として優れた特性をもつことを思い
出した。従来、Ｌａ１−！ＳｒｘＭｎ０３（ｘ≦ｏ、６
）系酸化物は室温近傍の電気抵抗が１ｏ 〜１ｏ Ω・
ｍの低い値を示す半導体として知られていたが、１００
０°Ｃまでの抵抗変化については検討されていす、発熱
体としての応用も試みられたことがなかったものである
。The inventors synthesized ceramics with various compositions, measured the temperature change in their electrical resistance from room temperature to 1000''C, and also examined the change in electrical resistance over time at high temperatures and the thermal shock resistance of the ceramics. La1-!SrxMn
I remembered that the composition of 03 series ceramics in the range of 0.16≦X≦0.8 has excellent properties as a heating element. Conventionally, La1-! SrxMn03(x≦o, 6
) system oxide has an electrical resistance of 1o to 1o Ω・near room temperature.
It was known as a semiconductor exhibiting a low value of m, but 100
Changes in resistance down to 0°C have not been studied, and application as a heating element has never been attempted.
次に、本発明の実施例について詳しく説明する。Next, embodiments of the present invention will be described in detail.
市販のＬａ２０３（純度９９．９９％）および試薬特級
のＳｒＣＯ３９ＭｎＣｏ３を準備し、下表に示す組成と
なるよう各々秤量した後、湿式ボールミルで２０時間混
合し、乾燥させて、ｒｏｏｏｏＣで２時間仮焼した。こ
の仮焼生成物を再び湿式ボールミルで２０時間粉砕した
後、乾燥し、さらに有機バインダーを加えて混合し、造
粒した後、加圧成型した。この成型物を空気中において
１４００’Ｃで２時間焼成し、焼結体試料を得た。ここ
で、まず電気抵抗ｉｌｌｌｌ試用試料て、第１図に示す
ように白金線１を埋込んだ成型体を焼結させて得た。こ
の試料２を電気炉中で室温から１ｏｏＯ°Ｃまで加熱し
ながら、それぞれについて室温および１０００″Ｃの抵
抗比、すなわち前述のａを測定した。その結果を表に示
す。Prepare commercially available La203 (purity 99.99%) and special reagent grade SrCO39MnCo3, weigh each to have the composition shown in the table below, mix in a wet ball mill for 20 hours, dry, and calcined in roooooC for 2 hours. did. This calcined product was pulverized again in a wet ball mill for 20 hours, then dried, an organic binder was added thereto, mixed, granulated, and then pressure molded. This molded product was fired in air at 1400'C for 2 hours to obtain a sintered body sample. First, an electric resistance trial sample was obtained by sintering a molded body in which a platinum wire 1 was embedded as shown in FIG. While heating this sample 2 from room temperature to 100°C in an electric furnace, the resistance ratio at room temperature and 1000''C, that is, the above-mentioned a, was measured for each sample.The results are shown in the table.
また、室温から１０００″Ｃでの電気抵抗の変化のいく
つかの例を従来例であるＳｉＣ，！：ＬａＣｒＯ３とと
もに第２図に示す。第２図では縦軸に室温の抵抗値で正
規化した抵抗値の対数をとり、横軸に温度をとって抵抗
の温度変化を示している。なお、符号は表の試料番号で
ある。In addition, some examples of changes in electrical resistance from room temperature to 1000"C are shown in Fig. 2 along with conventional examples of SiC,!:LaCrO3. In Fig. 2, the vertical axis shows the resistance value normalized by the resistance value at room temperature. The logarithm of the resistance value is taken, and the temperature is plotted on the horizontal axis to show the temperature change in resistance.The code is the sample number in the table.
（以 下 余 白 ）
＊は参照例
表および第２図からも明らかなように、Ｌ ａ １．Ｓ
ｒ ！Ｍ ｎ Ｏ３ｐ組成において、Ｉが０．１６未
満の組成およびＸがｏ、８を越える組成では室温と１０
０ｏ″Ｃの抵抗値の比ａが０．３以下となり、発熱体と
しては好ましくない。０．１６≦Ｘ≦０．８の範囲であ
れば、前述のａが０．３より大きく２より小さい発熱体
として好ましい特性を示す。また、第３図に示す形状の
発熱体３１を作製し、白金電極３２゜３２′間に通電す
ることにより室温と１０００”Ｃの冷熱サイクルを行い
、１ｏＯｏ時間後の抵抗変化率と割れの発生を調べた。(Margin below) *As is clear from the reference example table and Figure 2, L a 1. S
r! In the M n O3p composition, for compositions where I is less than 0.16 and compositions where X is more than o, 8, there is a difference between room temperature and 10
The ratio a of the resistance value of 0o''C is 0.3 or less, which is not preferable as a heating element.If the range is 0.16≦X≦0.8, the above-mentioned a is greater than 0.3 and less than 2. It exhibits desirable characteristics as a heating element.A heating element 31 having the shape shown in FIG. The rate of change in resistance and the occurrence of cracks were investigated.
この結果、！が０．９以上の試料では６００時間で割れ
が発生したが、他の組成では割れは発生せず、耐熱衝撃
性も十分あることがわかった。また、１０６ＣｙＲ間後
の抵抗変化率も２０％以内である。As a result,! Although cracks occurred after 600 hours in the samples with 0.9 or more, cracks did not occur in other compositions, indicating that they had sufficient thermal shock resistance. Further, the rate of change in resistance after 106 CyR is also within 20%.
以上のように、Ｌａ１−！ＳｒｘＭｎＯ３（０，１５≦
Ｘ≦０．８）は発熱体用セラミックス組成として優れた
性質を有していることがわかる。As mentioned above, La1-! SrxMnO3(0,15≦
It can be seen that X≦0.8) has excellent properties as a ceramic composition for a heating element.
図面は本発明にかかる発熱体用セラミック組成物につい
て説明するだめのもので、第１図は抵抗測定用試別の形
状を示す斜視図、第２図は本発明による発熱体の代表例
と従来例の温度による抵抗変化を対比させて示す曲線図
、第３図は耐久試験用試料の形状を示す平面図である。
代理人の氏名 弁理士 中 尾 敏 男 ほか１名”Ｉ
Ｍ屋（゛り
墨３１１１The drawings are only for explaining the ceramic composition for a heating element according to the present invention. Fig. 1 is a perspective view showing the shape of a sample for resistance measurement, and Fig. 2 shows a typical example of a heating element according to the invention and a conventional one. FIG. 3 is a curve diagram showing a comparison of the resistance change due to temperature in the example, and FIG. 3 is a plan view showing the shape of the durability test sample. Name of agent: Patent attorney Toshio Nakao and one other person”I
M-ya (゛ri-sumi 3111
Claims (1)
３（０，１５≦Ｘ≦０．８）の組成からなることを特徴
とする発熱体用セラミック組成物。Perovskite-type compound L al-! S r xMnO
3 (0.15≦X≦0.8).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56112495A JPS5815069A (en) | 1981-07-17 | 1981-07-17 | Ceramic composition for heating body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56112495A JPS5815069A (en) | 1981-07-17 | 1981-07-17 | Ceramic composition for heating body |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS5815069A true JPS5815069A (en) | 1983-01-28 |
Family
ID=14588072
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56112495A Pending JPS5815069A (en) | 1981-07-17 | 1981-07-17 | Ceramic composition for heating body |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5815069A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0265086A (en) * | 1988-08-30 | 1990-03-05 | Toshiba Lighting & Technol Corp | Heating element |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4976097A (en) * | 1972-11-27 | 1974-07-23 |
-
1981
- 1981-07-17 JP JP56112495A patent/JPS5815069A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4976097A (en) * | 1972-11-27 | 1974-07-23 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0265086A (en) * | 1988-08-30 | 1990-03-05 | Toshiba Lighting & Technol Corp | Heating element |
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