【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION
【０００１】[0001]
【産業上の利用分野】本発明は、抵抗材料に係り、特に
電気加熱の材料として抵抗率が１０-4〜１０5Ω・ｃｍ
と広範囲に制御できる材料とその製造法に関する。この
抵抗材料は、家電、食品、粉体、化学工業等の分野に利
用可能である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resistance material, and more particularly to a material for electric heating, having a resistivity of 10-4 to 105 Ω · cm.
And materials that can be controlled over a wide range, and their manufacturing methods. This resistance material can be used in fields such as home appliances, food, powder, and the chemical industry.
【０００２】[0002]
【従来の技術】電気加熱の熱量は（電流）2×（抵抗）
であり、抵抗は（抵抗率）×（抵抗体の長さ）／（抵抗
体の断面積）であることは周知の通りである。抵抗率は
材料固有の物性であり必要な熱量は長さ及び断面積を変
えることにより得る。一方、限定された表面積に必要な
熱量を投入したいとき、即ち、電力密度が指定されたと
きは抵抗率が適当な値を持つ材料を利用した方が便利で
ある。2. Description of the Related Art The amount of heat of electric heating is (current)2 × (resistance)
It is well known that the resistance is (resistivity) × (length of resistor) / (cross-sectional area of resistor). The resistivity is a physical property inherent to the material, and the required amount of heat can be obtained by changing the length and the cross-sectional area. On the other hand, when it is desired to input a necessary amount of heat to a limited surface area, that is, when a power density is specified, it is more convenient to use a material having an appropriate resistivity.
【０００３】しかし、金属系のそれは１０-4Ω・ｃｍオ
ーダであり小さすぎ、又セラミックス系発熱体、例えば
ＳｉＣは１０0〜１０-2Ω・ｃｍだが温度係数が正、負
混在の為不便である。又金属と絶縁物を混合して見掛け
上抵抗率を制御する方法があるが、絶縁物が多くなるほ
ど電気的に不連続になり、信頼性にかける欠点があっ
た。同様な考え方でカーボンを含有させた混合物もある
が、発熱体としては安全性に不安がある。また、抵抗率
が何ケタも異なる材料を混合した物質のそれは、パーコ
レーション理論よりある組成のところで急激な変化を起
すといわれているため、安定性に欠ける。[0003] However, metal-based materials are of the order of 10-4 Ω · cm, which are too small, and ceramic-based heating elements, for example, SiC, are 100 to 10-2 Ω · cm, but are inconvenient due to their positive and negative temperature coefficients. It is. There is also a method of apparently controlling the resistivity by mixing a metal and an insulator. However, as the number of insulators increases, the discontinuity becomes electrically discontinuous, and there is a drawback that reliability is increased. There is also a mixture containing carbon based on the same concept, but there is concern about safety as a heating element. In addition, a substance obtained by mixing materials having several orders of different resistivity has a lack of stability because it is said that a sudden change occurs at a certain composition according to the percolation theory.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、上記のよう
な従来技術の問題点を解決し、電力密度に適合させるた
めに、抵抗率を広範囲に制御できる抵抗材料を提供する
ことと、それを用いた抵抗率の制御法を提供することを
課題とする。SUMMARY OF THE INVENTION It is an object of the present invention to provide a resistive material capable of controlling the resistivity over a wide range in order to solve the above-mentioned problems of the prior art and adapt to the power density. An object of the present invention is to provide a method for controlling the resistivity using the method.
【０００５】[0005]
【課題を解決するための手段】上記課題を解決するため
に、本発明では、式、Ｌａ１−ｘ ＢａｘＣｏＯ３と
式、Ｂａ１−ｙＬａｙＴｉＯ３（式中、ｘは０．５以
上、ｙは１以下）との混合物からなる抵抗材料としたも
のである。また、本発明では、前記抵抗材料の製造方法
として、Ｌａ０．５Ｂａ０．５ＣｏＯ３ とＢａＴｉＯ
３ との粉体をモル比０．０５〜０．９５の範囲で混合
し、高温で反応させて製造することとしたものである。In order to solve the above problems SUMMARY OF THE INVENTION In the present invention,wherein, La 1-x Ba x CoO 3 andwherein, Ba 1-y La y TiO 3 ( where, x is 0. 5 above, y is obtained by a resistive material consistingof amixture of 1 or less). Further, in the present invention, method of producing the resistormaterial, and La0.5 Ba 0.5 CoO3 BaTiO
The powder3 is mixed in a range of molar ratio 0.05 to 0.95, in which was be prepared by reacting at elevated temperature.
【０００６】上記製造方法において、反応温度は８００
〜１５００℃の範囲がよい。さらに、前記抵抗材料にお
いては、原料モル比をそれぞれ変えることにより抵抗率
の相違する抵抗材料が得られるので、それらを任意に用
いることにより抵抗率を制御することができる。In the above production method, the reaction temperature is 800
The range of ~ 1500C is good. Further, in the above-mentioned resistance material, since the resistance materials having different resistivity can be obtained by respectively changing the molar ratios of the raw materials, the resistivity can be controlled by arbitrarily using them.
【０００７】[0007]
【作用】反応前の混合比、Ｌａ0.5Ｂａ0.5ＣｏＯ3を
０．４、ＢａＴｉＯ3を０．６用いて反応させ、その生
成物をＸ線回折した。Ｘ線回折パターンは斜方晶のＬａ
0.5Ｂａ0.5ＣｏＯ3系と正方晶のＢａＴｉＯ3系の混
合物として解析を行った。その結果の焼結体の格子定数
を表１に示す。[Action] before the reaction mixture ratio, La0.5 Ba0.5 CoO3 0.4, a BaTiO3 was reacted with 0.6 and the product was subjected to X-ray diffraction. X-ray diffraction pattern is orthorhombic La
The analysis was performed as a mixture of0.5 Ba0.5 CoO3 system and tetragonal BaTiO3 system. Table 1 shows the lattice constant of the resulting sintered body.
【０００８】[0008]
【表１】[Table 1]
【０００９】この結果から、Ｌａ０．５ Ｂａ０．５ Ｃ
ｏＯ３はＬａよりもイオン半径の大きいＢａがＬａと置
換して格子定数が増大したことから、Ｌａ1-ｘＢａｘ
ＣｏＯ3 のｘは０．５以上であり、またＢａＴｉＯ3 の
Ｂａが一部Ｌａと置換してＴｉ４＋がＴｉ３＋となり、
格子定数が変化して立方晶へと結晶系が転移したものと
推定された。従って、Ｂａ１−ｙＬａｙＴｉＯ３ の
ｙは１以下である。また、金属や半導体の抵抗係数は、
前者は“正”、後者は“負”であるが、本発明の抵抗材
料の内、ＢａＴｉＯ3 の混合比０．１〜０．２の間で生
成したそれは、抵抗の温度係数がほとんど変らないこと
が特徴点である。[0009] From thisresult, La0.5 Ba 0.5 C
In the case of oO3 , La having a larger ionic radius than La replaced La and the lattice constant increased, so that La1 -x Bax
X of CoO3 is 0.5 or more, and Ba of BaTiO3 partially replaces La with Ti4+ to become Ti3+ ,
It was presumed that the lattice system changed and the crystal system was changed to cubic.Therefore, y of the Ba1-y Lay TiO3 isbelow 1 or less. The resistance coefficient of metal or semiconductor is
The former "positive", while the latter isRu "negative" der, resistive material of the present invention
Among the materials , those produced at a mixing ratio of BaTiO3 of 0.1 to 0.2 are characterized by the fact that the temperature coefficient of resistance hardly changes.
【００１０】[0010]
【実施例】以下、本発明を実施例により具体的に説明す
るが、本発明はこの実施例に限定されるものではない。 実施例１ 出発物質としてＬａ0.5Ｂａ0.5ＣｏＯ3とＢａＴｉＯ
3を選んだ。前者の抵抗率は１０-4Ω・ｃｍ（室温）で
あり、後者は１０12Ω・ｃｍであるが、本研究では、原
子価制御してＰＴＣＲ効果を示すものを用いた。Ｌａ
0.5Ｂａ0.5ＣｏＯ3は、構成金属の硝酸塩水溶液から
共沈及び固相反応（１１５０℃、１２ｈ）法により調製
した。ＢａＴｉＯ3は、ＢａＴｉＯ（Ｃ2Ｏ4）・４Ｈ
2Ｏに０．２ｍｏｌ％のＳｂ3+を加えたものを１１５０
℃で６時間熱処理することにより調製した。それぞれの
粉体を所定のモル比でよく混合し、加圧成形（３ｔ／ｃ
ｍ2）後、１３５０℃、１時間焼結させた。焼結体を５
×３×１５ｍｍに整形した後、直流４端子法で抵抗率を
測定した。EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples. Example 1 La0.5 Ba0.5 CoO3 and BaTiO as starting materials
I chose3 . The former has a resistivity of 10−4 Ω · cm (room temperature), and the latter has a resistivity of 1012 Ω · cm. In the present study, a material having a PTCR effect by controlling the valence was used. La
0.5 Ba0.5 CoO3 was prepared from a nitrate aqueous solution of a constituent metal by coprecipitation and solid-phase reaction (1150 ° C., 12 h). BaTiO3 is made of BaTiO (C2 O4 ) .4H
1150 obtained by adding 0.2 mol% of Sb3+ to2 O
It was prepared by heat treatment at 6 ° C. for 6 hours. The respective powders are mixed well at a predetermined molar ratio, and then pressure-molded (3 t / c
After m2 ), sintering was performed at 1350 ° C. for 1 hour. 5 sintered bodies
After shaping to × 3 × 15 mm, the resistivity was measured by a DC four-terminal method.
【００１１】Ｌａ0.5Ｂａ0.5ＣｏＯ3とＢａＴｉＯ3
の混合比を１０：０，９：１，７：３，５：５，４：
６，８：２及び０：１０とした。抵抗率の測定は、２０
〜２５０℃で行った。直流４端子法で測定した試料抵抗
率を図１に示す。原子価制御したＢａＴｉＯ3を除きｌ
ｏｇρとＢａＴｉＯ3の混合比は線形となった。Ｌａ
0.5Ｂａ0.5ＣｏＯ3は測定温度範囲内で金属伝導性を
示すが、ＢａＴｉＯ3の混合比が０．３以上になると半
導体となった。なお、図中の数値はＢａＴｉＯ3の混合
比である。図２にＢａＴｉＯ3混合比０．６のＸ線回折
パターンを示す。La0.5 Ba0.5 CoO3 and BaTiO3
Of 10: 0, 9: 1, 7: 3, 5: 5, 4:
6, 8: 2 and 0:10. Measurement of resistivity is 20
Performed at ~ 250 ° C. FIG. 1 shows the sample resistivity measured by the DC four-terminal method. Except for BaTiO3 whose valence is controlled
The mixing ratio between ogρ and BaTiO3 became linear. La
0.5 Ba0.5 CoO3 shows metal conductivity within the measurement temperature range, but became a semiconductor when the mixing ratio of BaTiO3 became 0.3 or more. The numerical values in the figure are the mixing ratios of BaTiO3 . FIG. 2 shows an X-ray diffraction pattern at a BaTiO3 mixing ratio of 0.6.
【００１２】[0012]
【発明の効果】本発明の抵抗材料は、抵抗率が１０-4〜
１０5Ω・ｃｍのものが得られ、また、抵抗率の対数が
組成と線形関係となるので、目的に応じて、抵抗率を制
御でき、それぞれの分野に有効に利用できる。The resistance material of the present invention has a resistivity of 10-4 to 10-4 .
Since a resistivity of 105 Ω · cm is obtained, and the logarithm of the resistivity has a linear relationship with the composition, the resistivity can be controlled according to the purpose and can be effectively used in each field.
【図１】混合比を変えた場合の温度と抵抗率の関係を示
すグラフ。FIG. 1 is a graph showing the relationship between temperature and resistivity when the mixing ratio is changed.
【図２】ＢａＴｉＯ3混合比０．６のＸ線回折パターン
図。FIG. 2 is an X-ray diffraction pattern diagram with a BaTiO3 mixing ratio of 0.6.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特公 昭58−33191（ＪＰ，Ｂ１) (58)調査した分野(Int.Cl.7，ＤＢ名) H01C 7/00 - 17/30────────────────────────────────────────────────── ─── Continued on the front page (56) References JP-B-58-33191 (JP, B1) (58) Fields investigated (Int. Cl.7 , DB name) H01C7/ 00-17/30
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24217193AJP3307732B2 (en) | 1993-09-03 | 1993-09-03 | Resistive material and resistivity control method |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24217193AJP3307732B2 (en) | 1993-09-03 | 1993-09-03 | Resistive material and resistivity control method |
| Publication Number | Publication Date |
|---|---|
| JPH0774003A JPH0774003A (en) | 1995-03-17 |
| JP3307732B2true JP3307732B2 (en) | 2002-07-24 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24217193AExpired - Fee RelatedJP3307732B2 (en) | 1993-09-03 | 1993-09-03 | Resistive material and resistivity control method |
| Country | Link |
|---|---|
| JP (1) | JP3307732B2 (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6004617A (en)* | 1994-10-18 | 1999-12-21 | The Regents Of The University Of California | Combinatorial synthesis of novel materials |
| US5985356A (en)* | 1994-10-18 | 1999-11-16 | The Regents Of The University Of California | Combinatorial synthesis of novel materials |
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| JP5833191B1 (en) | 2014-06-25 | 2015-12-16 | 日本電信電話株式会社 | Distribution system and method |
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| JP5833191B1 (en) | 2014-06-25 | 2015-12-16 | 日本電信電話株式会社 | Distribution system and method |
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