JPS59101802A - Temperature sensitive resistance element - Google Patents
Temperature sensitive resistance elementInfo
- Publication number
- JPS59101802A JPS59101802A JP57210980A JP21098082A JPS59101802A JP S59101802 A JPS59101802 A JP S59101802A JP 57210980 A JP57210980 A JP 57210980A JP 21098082 A JP21098082 A JP 21098082A JP S59101802 A JPS59101802 A JP S59101802A
- Authority
- JP
- Japan
- Prior art keywords
- temperature
- resistance element
- sensitive resistance
- cobalt
- barium titanate
- 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
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 15
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 14
- 229910002113 barium titanate Inorganic materials 0.000 claims description 14
- 229910017052 cobalt Inorganic materials 0.000 claims description 10
- 239000010941 cobalt Substances 0.000 claims description 10
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 238000005245 sintering Methods 0.000 description 9
- 239000000843 powder Substances 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000011812 mixed powder Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 235000012054 meals Nutrition 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Thermistors And Varistors (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】
本発明は感温抵抗素子に係＃）１特に電力用の感温抵抗
素子に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a temperature-sensitive resistance element, and particularly to a temperature-sensitive resistance element for power use.
感温抵抗素子（正特性サーミスタ）は、抵抗が所定温度
以上になると急激に増大するセラミック半導体で、チタ
ン酸バリウムを基材とし、これに１価または３価の金属
酸化物をドープしてなシ、家！製品の分野においては、
定温匠発熱体、無接点スイッチ、定電流装置または電流
制限素子として使用されている。A temperature-sensitive resistance element (positive temperature coefficient thermistor) is a ceramic semiconductor whose resistance increases rapidly when the temperature rises above a certain temperature, and is made of barium titanate as a base material doped with a monovalent or trivalent metal oxide. Shi, home! In the field of products,
It is used as a constant temperature heating element, non-contact switch, constant current device or current limiting element.
しかし、上述した感温抵抗素子は、電力用（大電流用）
の限流素子として用いる場合には、常温における比抵抗
が１０ｇΩ・備程度と大きいために、通常の通電時にお
ける消費電力が過大となる問題があるとともに、セラミ
ックからなるために、事故時における短絡電流によル急
激に温度上昇して熱破壊する等の問題がおる。However, the above-mentioned temperature-sensitive resistance element is for power use (large current use)
When used as a current limiting element, the resistivity at room temperature is as large as 10 gΩ, which causes the problem of excessive power consumption during normal energization, and since it is made of ceramic, it is susceptible to short circuits in the event of an accident. There are problems such as rapid temperature rise due to current and thermal breakdown.
本発明は上述した問題に鑑みてなされたもので。The present invention has been made in view of the above-mentioned problems.
その目的とするところは、常温における比抵抗を小さく
しかつ機械的強度を高めることにより、電力用の限流素
子として使用し得るようにした感温抵抗素子の提供にあ
る。以下１図面を参照してこの発明の実施例全詳細に説
明する。The purpose is to provide a temperature-sensitive resistance element that can be used as a current-limiting element for electric power by reducing the specific resistance at room temperature and increasing the mechanical strength. Embodiments of the invention will now be described in detail with reference to the drawings.
本発明に係る感温抵抗素子は、たとえば回路中における
しゃ断器の負荷全軽減すべくその電源側に接続される電
力用限流素子として用いられるもので、チタン酸バリウ
ムの粉末に１〜３０重量％のコバルトの粉末を混合した
混合粉末の成形体を１真窒、還元性または不活性雰囲気
中において１１５０〜１５００℃の温度で焼結し、この
焼結体を酸化性雰囲気中において９００−１４００ ’
（：すｎヤ酸化処理してなる。The temperature-sensitive resistance element according to the present invention is used, for example, as a power current-limiting element connected to the power supply side in order to reduce the total load of a circuit breaker in a circuit, and is used as a power current-limiting element connected to the power supply side in order to reduce the total load of a breaker in a circuit. % of cobalt powder is sintered at a temperature of 1150 to 1500°C in a reducing or inert atmosphere, and the sintered body is sintered at a temperature of 900 to 1400°C in an oxidizing atmosphere. '
(: Sunya is oxidized.
ここで、チタン酸バリウムに対するコバルトの割合が８
０重量％を超える場合に七焼結が困難となるものであシ
、また、上述した範囲の温度で焼結することによシ、チ
タン酸バリウムの粉末中に介在されるコバルトの粉末が
、焼結を促進するとともに、結合剤として機能するため
に素子の機械的強度が高められるものである。さらに、
焼結体“を酸化処理するのは、素子の常温における比抵
抗Ｒ０に対する高温時の比抵抗島の比Ｒ１／Ｒ，ｉ高め
るためであるが、 １４００℃の温度を超えるとコバ
ルトが酸化して常温における比抵抗Ｒ，が高くなるので
避けなければならない。Here, the ratio of cobalt to barium titanate is 8
If the amount exceeds 0% by weight, sintering becomes difficult.Also, by sintering at the temperature in the above range, the cobalt powder interposed in the barium titanate powder can be It promotes sintering and also functions as a binder, thereby increasing the mechanical strength of the element. moreover,
The purpose of oxidizing the sintered body is to increase the ratio R1/R,i of the resistivity island at high temperature to the resistivity R0 of the element at room temperature, but if the temperature exceeds 1400°C, cobalt will oxidize. This should be avoided since the specific resistance R at room temperature becomes high.
上述した感温抵抗素子の製造は、まず１粒度１μｍ以下
が５０〜１００％であるチタン酸バリウムの粉末に純水
を加え、トれをプラスチック内張シ（テフロンコーティ
ング、）のボールミルに入れ、８〜１２ψのめのう制球
状玉石を用い、毎分７５〜８５Ｊ１転でボールミルを６
〜３０時間運転してｉ砕し、しかる後に１２０℃の突気
中で２昼夜以上乾燥して８０メジシユのｌ！全全通て一
３０メツシュのチタン酸バリウムの粉末を得る。To manufacture the above-mentioned temperature-sensitive resistance element, first, pure water is added to barium titanate powder whose particle size is 50 to 100% below 1 μm, and the mixture is placed in a ball mill with a plastic lining (Teflon coating). Using an agate spherical boulder of 8 to 12 ψ, run a ball mill at a speed of 75 to 85 J1 rotation per minute.
It was operated for ~30 hours, crushed, and then dried in a blast of air at 120°C for more than 2 days and nights to produce 80 meals. A total of 130 mesh barium titanate powder was obtained.
また、純度９９．９ｑ６のコバルトの粉末を３，５゜メ
ツシュｕｋｋして一３６０メツシュのコバルトの粉末全
書る。In addition, a cobalt powder with a purity of 99.9q6 is divided into 3.5 degrees mesh, and the total amount of cobalt powder with a purity of 1,360 mesh is written.
ついで、＝’ｇｏメツシュのチタン酸バリウムの粉末と
１〜３０重ｆｊｋｑｌＪの一３５０メツシュのコバルト
の粉末とをガラス製Ｖ型回転混合器によシア。Next, barium titanate powder of ='go mesh and cobalt powder of 1 to 30 mesh of 1350 mesh were sheared into a glass V-shaped rotary mixer.
ルコール（試薬特級エタノール）を用いて均一に混合さ
れるように８０〜６０分間混合し、しかる後にアルコー
ルを飛散、蒸発により除去して乾燥した混合粉末とする
。Alcohol (reagent special grade ethanol) is used to mix for 80 to 60 minutes to ensure uniform mixing, and then the alcohol is removed by scattering and evaporation to form a dry mixed powder.
上述した混合粉末を金型に入れるとともに２５０ｋｙ
／ ｃｎｌの圧力で加圧し、焼結による収縮を考慮した
所定の直径と厚さを有する円板状の成形体を作シ、この
成形体を磁器製（アルミナ）のサヤに入れ、不活性雰囲
気（アルゴンガス）中において１１５０〜１５００℃（
好ましくは１２５０〜１３５０℃）の温度で００５〜１
０時間かけて焼結する。The above-mentioned mixed powder was put into a mold and heated to 250 ky.
/ cnl pressure to produce a disc-shaped molded body with a predetermined diameter and thickness taking into account shrinkage due to sintering, and place this molded body in a porcelain (alumina) pod in an inert atmosphere. (argon gas) at 1150-1500℃ (
005-1 at a temperature of preferably 1250-1350°C)
Sinter for 0 hours.
なお、加熱、冷却時の昇降温速度は、３００℃／ｈ以下
で、２００℃／ｈが特性の安定化、生産性の面から適轟
である。また、焼結雰囲気は不活性雰囲気に限らす臭突
または還元性雰囲気（水素ガス）でもよいものである。The rate of temperature rise and fall during heating and cooling is 300° C./h or less, and 200° C./h is appropriate from the viewpoint of stabilizing properties and productivity. Further, the sintering atmosphere is not limited to an inert atmosphere, but may be an odor atmosphere or a reducing atmosphere (hydrogen gas).
最後に、上述した焼結体ｔ−を気中において９００〜１
４００℃の温度で０．６〜“１０時間かけて酸化処理す
ると所望の感温抵抗素子が完成する。Finally, the above-mentioned sintered body t- was placed in air at a temperature of 900 to 1
The desired temperature-sensitive resistance element is completed by oxidation treatment at a temperature of 400° C. for 0.6 to 10 hours.
なお、酸化処理時の昇降温速度は、焼結時の場合と同様
に８００℃／ｈ以下で行なわれるものである。Note that the rate of temperature rise and fall during the oxidation treatment is 800° C./h or less, as in the case of sintering.
ま°た、酸化処理の雰囲気は、を気に限らず酸紫すンチ
な突気中また酸素中等の酸化性雰囲気であれはよいもの
である。In addition, the atmosphere for the oxidation treatment is not limited to oxidation, but may be an oxidizing atmosphere such as an acidic atmosphere or an oxidizing atmosphere such as oxygen.
以上の製造方法によって得られた感温抵抗素子（直径３
９ ｍ／ｍ、厚さ１０ｍ／ｍ）の両面に、素体のＲ−Ｔ
％性に影響を与えるのを避けるべく工。The temperature-sensitive resistance element (diameter 3
9 m/m, thickness 10 m/m) on both sides of the element body.
In order to avoid affecting the percentage characteristics.
−Ｇ、の合金粉末ベーヌトヲ刷毛塗シして電極を形成し
て測定したＲ、−Ｔ特性の従来のものとの比較は第１図
に示すようになった。すなわち、第１図１は横軸に温度
Ｔ（℃）、縦軸に比抵抗Ｒ（Ω・ｃｍ ）會対数スケー
ル“ふったもので１曲線Ａで示すのは、チタン酸バリウ
ムの粉末の成形体を空気中において１２５０℃の温度で
１時間かけて焼結したものの、曲ｉＢ″ｔ′示すのは、
チタン酸バリウムの粉末の底形体をアルゴンガス中にお
いて１２５０℃の温度で１時間かけて焼結したもの、ま
た曲線Ｂ′で示すのは、チタン酸バリウムの粉末の成形
体をアルゴンガス中において１２５０℃の温度でｌＦ￥
ｊ間かけて焼結し、かつこの焼結体１ｆ−空気中におい
て１１５０℃の温度で１時間かけて酸化処理したもの、
そして。Figure 1 shows a comparison of the R and -T characteristics measured by brush-coating the -G alloy powder to form an electrode and comparing it with the conventional one. In other words, Fig. 1 shows temperature T (°C) on the horizontal axis and resistivity R (Ω cm ) on the vertical axis on a logarithmic scale. Curve A shows the molding of barium titanate powder. Although the body was sintered in air at a temperature of 1250°C for 1 hour, the curve iB″t′ shows:
Curve B' shows a shaped body of barium titanate powder sintered in argon gas at a temperature of 1250°C for 1 hour. lF￥ at a temperature of °C
j, and this sintered body 1f - oxidized in air at a temperature of 1150°C for 1 hour,
and.
曲線０で示すのは、チタン酸バウムとコバルトトの混合
粉末の成形体をアルゴンガス中において１２５０℃の温
度で１時間かけて焼結し、かつこの焼結体全空気中にお
いて１１５０℃の温度で１時間かけて酸化処理した本発
明に係るもののＲ−Ｔ％性である。Curve 0 indicates that a molded body of mixed powder of Baum titanate and Cobalt is sintered in argon gas at a temperature of 1250°C for 1 hour, and this sintered body is sintered at a temperature of 1150°C in whole air. This is the RT% property of the product according to the present invention which was oxidized for 1 hour.
したがって、本発明に係る感温抵抗素子の常温における
比抵抗は、約４０．ｃ’ａｔ程度となシ、従来のものに
比して約１／２δと小さくなることが判る。Therefore, the specific resistance of the temperature-sensitive resistance element according to the present invention at room temperature is about 40. It can be seen that it is about c'at, which is about 1/2 δ smaller than that of the conventional one.
また、本発明に係る感温抵抗素子は、チタン酸バリウム
に対するコバルトの添加（含有）割合（重量％）を変化
した場合（酸化処理； １１５０℃。Further, the temperature-sensitive resistance element according to the present invention can be obtained by changing the addition (containment) ratio (wt%) of cobalt to barium titanate (oxidation treatment; 1150°C).
１時間）、常温における比抵抗＆（Ω・ｃｍ）および常
温における。比抵抗＆に対するある温度（２４０℃）の
比抵抗Ｒ１（Ω・ｃｒｒＬ）の比Ｒ＋／Ｒ６は、それぞ
れ第２図（ａ）および第２図（ｂ）に示すようになった
。1 hour), specific resistance & (Ω cm) at room temperature and at room temperature. The ratio R+/R6 of the specific resistance R1 (Ω·crrL) at a certain temperature (240° C.) to the specific resistance & is shown in FIG. 2(a) and FIG. 2(b), respectively.
したがって、チタン酸バリウムに対するコバルトの含有
量は、１〜８０重量％が良好な結果をもたらすことが判
る。Therefore, it can be seen that a content of cobalt relative to barium titanate of 1 to 80% by weight brings about good results.
さらに１本発明に係る感温抵抗素子は、チタン酸バリウ
ムに対するコバルトの添加量を１０重量％とし、酸化処
理の温度Ｔ ＜”ｒ＝）を変化したｉ合、常温における
比抵抗＆に対するある温度（２４０℃）の比抵抗Ｒ１（
Ω・譚）の比Ｒ１／Ｒｅは、それぞれ第３因（ａ）およ
び第３図（ｂ）に示すようになった。Furthermore, in the temperature-sensitive resistance element according to the present invention, the amount of cobalt added to barium titanate is 10% by weight, and when the oxidation treatment temperature T<"r=) is changed, (240℃) specific resistance R1 (
The ratio R1/Re of Ω・tan) is shown in the third factor (a) and FIG. 3(b), respectively.
したかつ、て、酸化処理温度は９００〜１４００℃の範
囲が良好であることが判る。なお、１４００’Ｃｉ超え
ると常温における比抵抗凡が急激に大きくなるのは、コ
バルトの酸化のためである。Moreover, it is found that the oxidation treatment temperature is preferably in the range of 900 to 1400°C. The reason why the specific resistance at room temperature suddenly increases when 1400'Ci is exceeded is due to the oxidation of cobalt.
また、成形体の焼結温度Ｔ（’Ｃ）と素子の密度ｒ （
ｇ／ｃａ ）との関係は、第４図に示すようになった・
したがって、焼結温度は、１２５０〜１３５０℃の範囲
が好ま、シく、製品のコンパクト化を図シ得ることが判
る。In addition, the sintering temperature T ('C) of the compact and the density r (
The relationship between g/ca) is shown in Figure 4.
Therefore, it can be seen that the sintering temperature is preferably in the range of 1250 to 1350°C, and the product can be made more compact.
なお、感温抵抗素子の機械的強度の向上は、前述シた如
くコバルトがチタン酸バリウムの粒子を結合する結合剤
の役目を果すとともに、素子自体の熱伝導度の向上に寄
与し放熱効率が高められることによるものと思われる。The mechanical strength of the temperature-sensitive resistance element is improved because, as mentioned above, cobalt acts as a binder that binds barium titanate particles, and also contributes to improving the thermal conductivity of the element itself, improving heat dissipation efficiency. This seems to be due to being raised.
以上の如く本発明は、１〜３０重量％のコバルトを含有
するチタン酸バリウムの焼結体を酸化処理してなる感温
抵抗素子であるから、従来のものに比して常温における
比抵抗を大巾に小さくすることが−できるとともに１機
械的強度全向上することができ、ひいては電力用限流素
子として用いることができる等の効果を奏する。As described above, the present invention is a temperature sensitive resistance element formed by oxidizing a sintered body of barium titanate containing 1 to 30% by weight of cobalt. It has the advantage that it can be made much smaller in width, and its mechanical strength can be completely improved, and it can also be used as a current limiting element for electric power.
第１図は本発明に係る感温抵抗素子と従来のものとを比
較したＲ−Ｔ特性図、第２図（ａ）および第２図（ｂｌ
はそれぞれチタン酸バリウムに対するコバルトの含有割
合全変化した場合の常温における比抵抗および常温に゛
おける比抵抗に対する所定温度における比抵抗の比を表
わした特性図、第３１ｇ （ａ）および第８ ［ｋｌ
（ｂ）はそれぞれ酸化処理温度を変化した場合の常温に
おける比抵抗および常温における比抵抗に対する所定温
度における比抵抗や比？表わした特性図、第４９は焼結
温度と素子の密度との関係を表わした特性図である。
第１図
第３図（ａ）
第３図（ｂ’）
第２図（ａ）
Ｍ４図
Ｐ【
Ｔ （’Ｃ）Fig. 1 is an RT characteristic diagram comparing the temperature sensitive resistance element according to the present invention with a conventional one, Fig. 2(a) and Fig. 2(bl
31g (a) and 8th [kl
(b) is the specific resistance at room temperature when the oxidation treatment temperature is changed, and the specific resistance and ratio at a given temperature to the specific resistance at room temperature? Characteristic diagram No. 49 is a characteristic diagram showing the relationship between sintering temperature and element density. Figure 1 Figure 3 (a) Figure 3 (b') Figure 2 (a) M4 Figure P [ T ('C)
Claims (1)
の焼結体全酸化処理してなる感温抵抗素子。A temperature-sensitive resistance element formed by fully oxidizing a sintered body of barium titanate containing 1 to 30 zi% cobalt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57210980A JPS59101802A (en) | 1982-12-01 | 1982-12-01 | Temperature sensitive resistance element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57210980A JPS59101802A (en) | 1982-12-01 | 1982-12-01 | Temperature sensitive resistance element |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS59101802A true JPS59101802A (en) | 1984-06-12 |
Family
ID=16598308
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57210980A Pending JPS59101802A (en) | 1982-12-01 | 1982-12-01 | Temperature sensitive resistance element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59101802A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59220902A (en) * | 1983-05-31 | 1984-12-12 | 株式会社明電舎 | Temperature sensitive resistance element |
-
1982
- 1982-12-01 JP JP57210980A patent/JPS59101802A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59220902A (en) * | 1983-05-31 | 1984-12-12 | 株式会社明電舎 | Temperature sensitive resistance element |
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