JPS62288159A - Composite oxide sintered body and ceramic heater - Google Patents
Composite oxide sintered body and ceramic heaterInfo
- Publication number
- JPS62288159A JPS62288159A JP61129856A JP12985686A JPS62288159A JP S62288159 A JPS62288159 A JP S62288159A JP 61129856 A JP61129856 A JP 61129856A JP 12985686 A JP12985686 A JP 12985686A JP S62288159 A JPS62288159 A JP S62288159A
- Authority
- JP
- Japan
- Prior art keywords
- infrared
- sintered body
- composite oxide
- oxide sintered
- ceramic
- 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.)
- Granted
Links
- 239000002131 composite material Substances 0.000 title claims description 30
- 239000000919 ceramic Substances 0.000 title description 29
- 239000000203 mixture Substances 0.000 claims description 18
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 description 31
- 229910010293 ceramic material Inorganic materials 0.000 description 18
- 230000005855 radiation Effects 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- 239000011572 manganese Substances 0.000 description 8
- 239000010936 titanium Substances 0.000 description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 239000007769 metal material Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000011575 calcium Substances 0.000 description 5
- 230000005611 electricity Effects 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- -1 ditania Chemical compound 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 229910001120 nichrome Inorganic materials 0.000 description 1
- 239000000615 nonconductor Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000007569 slipcasting Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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】
３、発明の詳細な説明
（産業上の利用分野）
本発明は第一に、（Ｃａ、Ｓｒ）（Ｍｎ、Ｔｉ ）Ｏ３
系ペロブスカイト型＠造をもつ導電性複合酸化物焼結体
に関し、第二に前記導電性複合酸化物焼結体を主成分と
するセラミックス発熱体に関する。Detailed Description of the Invention 3. Detailed Description of the Invention (Field of Industrial Application) The present invention firstly provides (Ca, Sr) (Mn, Ti) O3
The present invention relates to a conductive composite oxide sintered body having a perovskite type structure, and secondly relates to a ceramic heating element having the conductive composite oxide sintered body as a main component.
最近、水分の乾燥や揮発性有機物の蒸発などに赤外線ヒ
ータが広く利用されている。とりわ【プ、主として赤外
線を放射する赤外線ヒータは、赤外線が水や有機物によ
く吸収され、不必要な化学反応を及ぼすことなく熱エネ
ルギーに変換される利点から食品分野、化学分野、木材
、繊維分野などに加熱、乾燥装置として幅広く利用され
つつある。Recently, infrared heaters have been widely used for drying moisture and evaporating volatile organic substances. Infrared heaters, which mainly emit infrared rays, are used in the food field, chemical field, wood, and textiles because of the advantage that infrared rays are well absorbed by water and organic substances and converted into thermal energy without causing unnecessary chemical reactions. It is becoming widely used as heating and drying equipment in various fields.
しかしながら、従来赤外線ヒータの発熱材料としては一
般にニクロムや或いは白金やカンクル等の金属材料が用
いられ、これらの金属材料では特に長波長の赤外線波長
域になる程、発熱体からの熱放射効率が低下してしまう
。However, conventional infrared heaters generally use metal materials such as nichrome, platinum, and cankle as the heat generating material, and with these metal materials, the efficiency of heat radiation from the heating element decreases, especially in the longer infrared wavelength range. Resulting in.
このため、赤外線波長域での熱放射エネルギーを金属発
熱体から充分に得るためには、金属発熱体の表面温度を
より高温にして赤外線エネルギー放射強度を高めること
によっていた。その結果、従来の赤外線ヒータでは金属
発熱体を高温に加熱しなければならず多大なエネルギー
を消費し、同時に金属発熱体の寿命を短かくしてしまう
という問題を有していた。Therefore, in order to obtain sufficient thermal radiation energy in the infrared wavelength range from the metal heating element, the surface temperature of the metal heating element has been raised to a higher temperature to increase the infrared energy radiation intensity. As a result, conventional infrared heaters have the problem of having to heat the metal heating element to a high temperature, consuming a large amount of energy, and at the same time shortening the life of the metal heating element.
これに対し、最近、赤外線ヒータに各種のセラミックス
を利用する研究が進められている。セラミックス材料は
、金属材料に比較して一般に赤外線放射特性が優れてお
りアルミナ、ジルコニア、ヂタニア、ムライト、コーデ
ィエライト、β−スポンジュメン等のセラミックスを赤
外線放射材料とした赤外線ヒータが開発されている。In response, research has recently been underway to utilize various ceramics for infrared heaters. Ceramic materials generally have better infrared radiation characteristics than metal materials, and infrared heaters have been developed using ceramics such as alumina, zirconia, ditania, mullite, cordierite, and β-spondumene as infrared radiation materials.
（発明が解決しようとする問題点）
上記の如くセラミックス材料は、赤外線波長域での熱放
射効率が金属材料にくらべて優れている。(Problems to be Solved by the Invention) As described above, ceramic materials have better heat radiation efficiency in the infrared wavelength region than metal materials.
この点からセラミックス赤外線ヒータが最近注目され、
従来の金属発熱体による赤外線加熱ヒータを買換しつつ
ある。From this point of view, ceramic infrared heaters have recently attracted attention.
People are replacing their conventional infrared heaters with metal heating elements.
しかしながら、従来のセラミックス材料では、一般に電
気絶縁体でおり導電性が劣っている。このため、セラミ
ックス材料自体に通電し、セラミックス材料を自己発熱
させることが難しい。そこで、セラミックスを利用した
従来のセラミックス赤外線ヒータでは、金属材料を発熱
体として用い、その外側をセラミックスで覆ったいわゆ
る二重構造をとっている。即ち、金属発熱体の発熱エネ
ルギーは一旦セラミックスに吸収され、セラミックスが
間接加熱されることにより、セラミックスから熱エネル
ギーを放射するようにされていた。その結果、セラミッ
クスを加熱する為の金属発熱体については゛それ自体の
エネルギー効率が何ら改善されないものである。また、
二重＠造をとるために赤外線ヒータの構造自体が複雑化
してしまうという問題を有していた。However, conventional ceramic materials are generally electrical insulators and have poor electrical conductivity. For this reason, it is difficult to apply electricity to the ceramic material itself and cause the ceramic material to self-heat. Therefore, conventional ceramic infrared heaters using ceramics have a so-called double structure in which a metal material is used as a heating element and the outside is covered with ceramics. That is, the heat generation energy of the metal heating element is once absorbed by the ceramics, and the ceramics are indirectly heated so that the heat energy is radiated from the ceramics. As a result, the energy efficiency of the metal heating element itself for heating ceramics is not improved at all. Also,
There was a problem in that the structure of the infrared heater itself became complicated due to the double structure.
一方、近年プラスチックス等の有機材料や、食品、木材
など各種の物体の電磁波に対する吸収波長域の研究が進
み、赤外線の中でも２０．５μｍから２５μｍ以上にも
至る遠赤外線がこれらの材料の優れた吸収波長域である
ことがわかってきた。On the other hand, in recent years, research has progressed on the absorption wavelength range of electromagnetic waves of various objects such as organic materials such as plastics, food, and wood. It has become clear that this is the absorption wavelength region.
これらの遠赤外線は物体に最もよく吸収され、内部まで
均一に加熱できる優れた特性をもっている。These far infrared rays are best absorbed by objects and have the excellent property of uniformly heating the inside of objects.
しかるに、従来のセラミックス材料によると、遠赤外線
波長域での熱放射エネルギーは金属材料にくらべて優れ
ているものの、一般に１５μｍ以上の遠赤外線領域では
赤外線エネルギー放射強度が低下してしまう。特に、１
５μｍ以上の遠赤外線波長域で０．９以上のエネルギー
放射率を得るセラミックス材料は知られていなかった。However, although conventional ceramic materials have superior thermal radiation energy in the far-infrared wavelength region compared to metal materials, the infrared energy radiation intensity generally decreases in the far-infrared region of 15 μm or more. In particular, 1
A ceramic material that has an energy emissivity of 0.9 or more in a far-infrared wavelength region of 5 μm or more has not been known.
このため、セラミックス赤外線ヒータの熱効率を一層改
善する為には、波長が１５μｍ以上の波長域でもエネル
ギー放射率が０．９以上を有するセラミックス材料の開
発が望まれていた。Therefore, in order to further improve the thermal efficiency of ceramic infrared heaters, it has been desired to develop a ceramic material that has an energy emissivity of 0.9 or more even in a wavelength range of 15 μm or more.
本発明は、上記の従来技術の有していた問題点を解決す
るために、第一に導電性を有するとともに遠赤外線波長
域でも優れたエネルギー放射率を有する新なセラミック
ス材料を提供することを目的とし、第二にかかる新なセ
ラミックス材料の特性な性質を利用した、筒車な＠造で
エネルギー効率に優れたセラミックス赤外線ヒータを実
現できるセラミックス発熱体を提供することを目的とす
る。In order to solve the problems of the above-mentioned prior art, the present invention aims to provide a new ceramic material that is electrically conductive and has excellent energy emissivity even in the far-infrared wavelength range. The second object of the present invention is to provide a ceramic heating element that makes use of the special properties of the new ceramic material and can realize a ceramic infrared heater with an hour wheel structure and excellent energy efficiency.
本発明は上記目的を達成するために第一に、ｌＣａＭｎ
０３ ＶＳｒＭｎ ０３−ｚＣａ Ｔｉ Ｏ３のペ
ロブスカイト型構造をもつ複合酸化物焼結体において、
上記組成範囲を、χを３０乃至９０モル％、ｙ＠ｏ乃至
３０モル％、２を５乃至４０モル％として複合酸化物焼
結体を構成するものである。更に、本発明の第二は、ｌ
ＣａＭｎ ０３ ｙｓｒＭｎ ０３−ｚＣａ Ｔｉ
０３のχを３０乃至９０モル％、ｙをＯ乃至３０モル％
、２を５乃至４０モル％としたペロブスカイト型構造の
導電性複合酸化物焼結体を主成分としてセラミックス発
熱体を構成するものである。In order to achieve the above objects, the present invention firstly provides lCaMn
In a composite oxide sintered body having a perovskite structure of 03 VSrMn 03-zCa Ti O3,
The composite oxide sintered body is constructed by setting the above composition range to be 30 to 90 mol% for χ, 30 to 30 mol% for y@o, and 5 to 40 mol% for 2. Furthermore, the second aspect of the present invention is l
CaMn 03 ysrMn 03-zCa Ti
χ of 03 is 30 to 90 mol%, y is O to 30 mol%
, 2 is contained in an amount of 5 to 40 mol % in a conductive composite oxide sintered body having a perovskite structure as a main component.
上記構成によれば第一に、上記組成比によって構成され
た（Ｃａ 、Ｓｒ ）（Ｍｎ 、Ｔｉ ）Ｏ３系ペロブ
スカイ１〜型構造をもつ複合酸化物焼結体は幅広い固溶
領域をもつため上記組成比範囲内でその組成比を変える
ことにより目的に合わせて導電性を幅広く変化させるこ
とができる。また、上記組成範囲における上記焼結体は
、赤外線波長域の特に波長か１５μｍ以上の遠赤外線領
域において０．９以上の赤外線放射率を有するので、高
いエネルギー効率で遠赤外線を放射することが可能であ
る。According to the above configuration, firstly, the composite oxide sintered body having the (Ca, Sr) (Mn, Ti) O3-based perovskie 1-type structure constituted by the above composition ratio has a wide solid solution region. By changing the composition ratio within the composition ratio range, the conductivity can be varied widely depending on the purpose. In addition, the sintered body in the above composition range has an infrared emissivity of 0.9 or more in the infrared wavelength region, particularly in the far infrared region with a wavelength of 15 μm or more, so it can emit far infrared rays with high energy efficiency. It is.
第二に、上記組成比によって構成された（Ｃａ。Secondly, (Ca.
Ｓｒ ）（Ｍｎ 、’Ｔｉ ）Ｏ３系ペロブスカイ１〜
型構造をもつ複合酸化物焼結体は、焼結体自体が優れた
導電性をもつセラミックス材料でおるので、焼結体自体
を直接通電して加熱させることができる。Sr)(Mn,'Ti)O3-based perovsky 1~
Since the composite oxide sintered body having a mold structure is made of a ceramic material with excellent conductivity, the sintered body itself can be heated by directly applying electricity.
しかも、遠赤外線波長域において０．９以上の高いエネ
ルギー放射率を有するので発熱体に用いた場合にはエネ
ルギー効率を高める作用をなす。従って、上記焼結体を
主成分とすることにより広範囲の赤外線を高効率に放射
できるセラミックス発熱体を実現することができるもの
でおる。Furthermore, since it has a high energy emissivity of 0.9 or more in the far-infrared wavelength region, it has the effect of increasing energy efficiency when used in a heating element. Therefore, by using the above-mentioned sintered body as a main component, it is possible to realize a ceramic heating element that can radiate a wide range of infrared rays with high efficiency.
［実施例］
以下、第１図、第２図及び第３図を参照して第１゛の発
明の詳細な説明する。[Example] Hereinafter, the first invention will be described in detail with reference to FIGS. 1, 2, and 3.
原料としては通常に入手しうる炭酸カルシウム（ＣａＣ
Ｏ３）、炭酸ストロンチウム（Ｓｒ ｃｏ３ ＞ 、Ｗ
化マンガン（Ｍｎ Ｏ２＞及び酸化チタニウム（Ｔｉ
０２ ）を用いた。Calcium carbonate (CaC), which is commonly available, is used as a raw material.
O3), strontium carbonate (Sr co3 >, W
Manganese oxide (Mn O2) and titanium oxide (Ti
02) was used.
上記原料は秤量して各種の配合比となるように混合した
。上記原料主成分の代表的な配合比の例を実施例１乃至
実施例１２とし、第１図に特性表として示す。The above raw materials were weighed and mixed at various blending ratios. Examples of typical blending ratios of the main ingredients of the raw materials are shown in Examples 1 to 12 as a characteristic table in FIG.
混合物は１１００乃至１２００’Ｃで３時間の仮焼を行
った。その後、仮焼した混合物をボールミルで湿式粉砕
した。粉砕した粉砕粉は、乾燥したのちもう一度上記仮
焼の場合と同じ焼成条件で仮焼を行った。これは、均質
な固溶体の生成を行わしめるためである。The mixture was calcined at 1100 to 1200'C for 3 hours. Thereafter, the calcined mixture was wet-pulverized using a ball mill. The pulverized powder was dried and then calcined again under the same firing conditions as in the above calcining. This is to generate a homogeneous solid solution.
上記によって得た合成粉末はバインダーを加えたのち加
圧成形し、各種の成形体とした。なお、バインダーとし
ては実施例ではポリビニールアルコール水溶液を用いた
。The synthetic powder obtained above was press-molded after adding a binder to form various molded bodies. In addition, as a binder, a polyvinyl alcohol aqueous solution was used in the examples.
成形体の形状は、電気抵抗測定用試料には直径１２＃、
厚さ２ｍの円板状形状とし、また、赤外線放射率測定用
試料としては直径４０ｍ、厚さ３ｍの円板状形状とした
。これらの成形体はアルミナ磁器製の容器に入れて、１
１００乃至１３５０℃で３時間の本焼成を行った。これ
によって（Ｃａ、３ｒ ＞ （Ｍｎ、 Ｔｉ ）Ｏ３
系のベロアスカイ１〜型構造をもつ複合酸化物焼結体を
得た。The shape of the molded body is 12# in diameter for the sample for electrical resistance measurement.
The sample was shaped like a disk with a thickness of 2 m, and the sample for infrared emissivity measurement was shaped like a disk with a diameter of 40 m and a thickness of 3 m. These molded bodies were placed in an alumina porcelain container and 1
Main firing was performed at 100 to 1350°C for 3 hours. As a result, (Ca, 3r > (Mn, Ti)O3
A composite oxide sintered body having a velor sky 1-type structure was obtained.
上記焼結体は、ｘｃａ Ｍｎ Ｏ３−
ｙＳｒＭｎ０３ ＺＣａＴ１０３の肴造式においてχ
を３０乃至９０モル％、ｙをＯ乃至３０モル％、Ｚを５
乃至４０モル％の組成範囲としたもので、上記組成範囲
において幅広い固溶領域を持つとともに、特有な電気導
電性と高い赤外線放射率を示すものであった。第１図の
示した各種の実施例についての比抵抗と赤外線放射率の
測定結果を、同表の比抵抗間及び赤外線放射率の欄に示
した。The above sintered body is
30 to 90 mol%, y to 30 mol%, Z to 5
The composition range was from 40 mol % to 40 mol %, and it had a wide solid solution range within the above composition range, and also exhibited unique electrical conductivity and high infrared emissivity. The measurement results of resistivity and infrared emissivity for the various examples shown in FIG. 1 are shown in the resistivity and infrared emissivity columns of the same table.
なお、上記複合酸化物焼結体についての電気抵抗測定は
、交流ブリッジによって行い、測定周波数は１０ＫＨ２
とした。The electrical resistance of the composite oxide sintered body was measured using an AC bridge, and the measurement frequency was 10KH2.
And so.
第１図には室温における比抵抗値を示しであるが、上記
組成範囲内では、いずれの実施例も数Ωｃｍ乃至数十Ω
ｃｍの比抵抗を有している。一方、上記組成範囲外では
比抵抗が極端に大きくなるか、あるいは極端に小さくな
る。Figure 1 shows the specific resistance value at room temperature, but within the above composition range, all Examples range from several Ωcm to several tens of Ω.
It has a specific resistance of cm. On the other hand, outside the above composition range, the specific resistance becomes extremely large or extremely small.
即ち、本発明に係る複合酸化物焼結体は、上記組成範囲
内では種々の応用目的に適した広い組成選択性と安定性
とを有しており、例えば−上記焼結体は、発熱体ヒータ
として用いる目的に極めて適した導電性セラミックス材
料であることがわかる。That is, the composite oxide sintered body according to the present invention has wide composition selectivity and stability suitable for various application purposes within the above composition range. It can be seen that the conductive ceramic material is extremely suitable for use as a heater.
第２図に、第１図中の実施例２，５．８及び１２につい
ての比抵抗温度特性図を示す。図におい−（、縦軸は比
抵抗値を指数表示し、横軸は測定雰囲気温度を逆数表示
している。いずれの実施例も室温から８００℃以上迄の
広い温度範囲にわたって安定な負性の抵抗温度特性を示
している。FIG. 2 shows resistivity temperature characteristic diagrams for Examples 2, 5.8, and 12 in FIG. 1. In the figure, the vertical axis represents the specific resistance value as an index, and the horizontal axis represents the measurement atmosphere temperature as a reciprocal. Shows resistance temperature characteristics.
次に、上記複合酸化物焼結体についての赤外線放射率は
、下記によりダブルビームの光学的零位法によって求め
た。即ら、焼結体試料を５００′Ｇに加熱し、黒体炉の
放射率を１としたときの前記試料の示差赤外線放射スペ
クトルを求め、それから赤外線放射率を算出する方法で
ある。Next, the infrared emissivity of the composite oxide sintered body was determined by the double beam optical zero method as described below. That is, the method is to heat a sintered sample to 500'G, obtain the differential infrared radiation spectrum of the sample when the emissivity of the blackbody furnace is set to 1, and then calculate the infrared emissivity.
上記ににつて求めた各実施例についての赤外線放射率値
を第１図に示しておる。上記組成範囲内ではいずれの実
施例も波長１５μｍ以上の波長域での赤外線放射率が０
．９以上でめった。特に、実施例１１ては０．９５にも
至る高い放射率を示している。The infrared emissivity values for each example determined above are shown in FIG. Within the above composition range, the infrared emissivity in the wavelength range of 15 μm or more is 0 in all Examples.
．． 9 or more is rare. In particular, Example 11 shows a high emissivity of up to 0.95.
第３図に、第１図中の実施例１１についての赤外線放射
率の波長特性図を、従来の他の赤外線発熱体等との比較
において示す。図において縦軸は赤外線放射率を示し、
横軸は波長を示している。FIG. 3 shows a wavelength characteristic diagram of infrared emissivity for Example 11 in FIG. 1 in comparison with other conventional infrared heating elements. In the figure, the vertical axis shows infrared emissivity,
The horizontal axis shows wavelength.
赤外線光源として広く用いられている赤外線ランプでは
、図示の如く波長５μｒｎ以上においてほとんど放射率
が零に近くなってしまい、いわゆる遠赤外線を放射して
いない。また、遠赤外線ヒータとして広く用いられてい
る石英ヒータも、はず同様に遠赤外線領域での放射率が
急激に低下している。更に、最近注目されているセラミ
ックス材料を用いたジルコニア系ヒータは、遠赤外線領
域で比較的高い放射率を示しているが、波長５μｍ迄の
領域では放射率が０．９以下にとどまっている。As shown in the figure, infrared lamps widely used as infrared light sources have an emissivity close to zero at wavelengths of 5 μrn or more, and do not emit so-called far-infrared rays. Furthermore, the emissivity of quartz heaters, which are widely used as far-infrared heaters, also rapidly decreases in the far-infrared region. Furthermore, zirconia-based heaters using ceramic materials, which have recently attracted attention, exhibit relatively high emissivity in the far-infrared region, but the emissivity remains at 0.9 or less in the region of wavelengths up to 5 μm.
なお、ジルコニア系ヒータでは、ジルコニア系セラミッ
クス材料は比較的優れた赤外線放射率をもつものの、絶
縁体であるので、セラミックス自体に通電して自己発熱
することができないという欠点をもっている。これに対
して、本発明に係る複合酸化物焼結体は、波長１５μｍ
迄の範囲やそれ以上の遠赤外線領域においても０．９以
上の高い赤外線放射率を有し、しかも前記の如く優れた
導電性を備えたものである。In the case of a zirconia heater, although the zirconia ceramic material has a relatively high infrared emissivity, since it is an insulator, it has the disadvantage that it cannot self-heat by applying electricity to the ceramic itself. On the other hand, the composite oxide sintered body according to the present invention has a wavelength of 15 μm.
It has a high infrared emissivity of 0.9 or more even in the far infrared region above and above, and has excellent conductivity as described above.
即ら、本発明に係る複合酸化物焼結体は、例えば赤外線
放射材料として用いる場合には極めて高効率に赤外線を
放射することができ、セラミックス赤外線ヒータ用の材
料としての応用目的に適した優れたセラミックス材料で
あることがわかる。That is, the composite oxide sintered body according to the present invention can emit infrared rays with extremely high efficiency when used, for example, as an infrared radiation material, and is an excellent material suitable for application as a material for ceramic infrared heaters. It can be seen that it is a ceramic material.
次に、第２の発明の実施例を以下に説明する。Next, an embodiment of the second invention will be described below.
本実施例は、前記第１の発明の実施例に係る複合酸化物
焼結体を主成分とし、前記焼結体の特有な導電性と高い
赤外線放射率との特有な性質を専ら利用するセラミック
ス発熱体に関する。実施例における複合酸化物焼結体の
製法、材料主成分配合比等は前記第１の発明の実施例と
異なるものではない。なお、前記第１の発明の詳細な説
明では、成形形状を円板状とし、特に電気特性や赤外線
放射率の測定試料として適したものとして説明したが、
本実施例に係るセラミックス発熱体では、成形形状の一
例が円柱状である。また、円柱状焼結体の両端部には電
極部分を設けている。比抵抗が１Ωｃｍ程度の複合酸化
物焼結体を主成分として形成した直径１ ｃｍ、長さ２
５ｃｍのセラミックス発熱体は、約３０Ωの抵抗を有し
、１００Ｖ電源を印加すると約３００Ｗの発熱体を構成
する。This example is a ceramic material that has the composite oxide sintered body according to the example of the first invention as a main component and exclusively utilizes the unique properties of the sintered body, such as its unique conductivity and high infrared emissivity. Regarding heating elements. The manufacturing method of the composite oxide sintered body, the blending ratio of the main components of the materials, etc. in the examples are not different from the examples of the first invention. In addition, in the detailed explanation of the first invention, the molded shape was described as a disk shape, and it was explained that it was particularly suitable as a measurement sample for electrical properties and infrared emissivity.
In the ceramic heating element according to this embodiment, an example of the molded shape is a columnar shape. Further, electrode portions are provided at both ends of the cylindrical sintered body. Diameter 1 cm, length 2 made mainly of composite oxide sintered body with specific resistance of about 1 Ωcm
A 5 cm ceramic heating element has a resistance of about 30Ω, and when a 100V power source is applied, it constitutes a heating element of about 300W.
なあ、本発明により構成されるセラミックス発熱体は、
必ずしも全体が上記複合酸化物焼結体により構成される
必要はなく、セラミックス発熱体の主成分に上記第１の
発明に係る複合酸化物焼結体が主成分として用いられて
いればよい。即ち、他のセラミックス材料や導電材料等
の材と通常の技術において組合せて用いることができる
。By the way, the ceramic heating element constructed according to the present invention is
The entire ceramic heating element does not necessarily have to be composed of the composite oxide sintered body as long as the composite oxide sintered body according to the first aspect of the invention is used as the main component. That is, it can be used in combination with other ceramic materials, conductive materials, etc. using conventional techniques.
また、セラミックス発熱体は上記形状に限られることな
く、平板状、円筒状など自由な形状に形成できるもので
ある。Further, the ceramic heating element is not limited to the above shape, but can be formed into any shape such as a flat plate or a cylinder.
上記セラミックス発熱体は、第１の発明に係る複合酸化
物焼結体が導電性を有するので、複合酸化物自体に通電
して自己発熱させることができる。Since the composite oxide sintered body according to the first invention has conductivity, the ceramic heating element can self-heat by supplying electricity to the composite oxide itself.
これにより、従来の絶縁性セラミックス材料を用いるセ
ラミックス発熱体と異なり、別個な発熱体としての金属
ヒータなどを必要とせず、いわゆる二重構造の要がない
、その結果、セラミックス発熱体の構造を極めて簡単に
する優れた効果を生む。As a result, unlike ceramic heating elements that use conventional insulating ceramic materials, there is no need for a metal heater as a separate heating element, and there is no need for a so-called double structure.As a result, the structure of ceramic heating elements can be improved. It's simple and produces great results.
また、本発明の複合酸化物焼結体は遠赤外領域でも高い
赤外線放射率を有している。その結果、本発明のセラミ
ックス発熱体は高効率に実用価値の高い遠赤外線を放射
でき、エネルギー利用効率を格段に高める効果を生む。Further, the composite oxide sintered body of the present invention has high infrared emissivity even in the far infrared region. As a result, the ceramic heating element of the present invention can radiate far-infrared rays of high practical value with high efficiency, producing the effect of significantly increasing energy utilization efficiency.
なお、上記実施例の説明において、原料を炭酸カルシウ
ム、炭酸ス１〜ロンチウム、酸化マンガン及び酸化チタ
ニウムとしたが、これに限られることなく通常の技術的
手段として用いられる他のこれら金属の化合物とするこ
ともできる。また、粉砕方法を湿式ボールミルとして説
明したがそれに限らず、乾式粉砕とすることや振動ミル
などの他の粉砕方法を用いることもできる。更に、バイ
ングーとしてポリビニールアルコール水溶液を例示した
が、これに限られず、他の通常用いうる各種の粘結剤を
用いうろことは勿論である。また、上記実施例では加圧
成形による粉体成形を例として示したが、他のスリップ
キャスティング法など各種の成形方法を用いることもで
きる。In the description of the above examples, the raw materials were calcium carbonate, rontium carbonate, manganese oxide, and titanium oxide, but the raw materials are not limited thereto, and other compounds of these metals used as ordinary technical means may be used. You can also. Furthermore, although the pulverization method has been described as a wet ball mill, it is not limited thereto, and other pulverization methods such as dry pulverization or a vibration mill can also be used. Further, although an aqueous polyvinyl alcohol solution has been exemplified as the binder, the present invention is not limited to this, and it goes without saying that various other commonly used binders may be used. Further, in the above embodiments, powder molding by pressure molding was shown as an example, but various molding methods such as other slip casting methods can also be used.
（発明の効果〕
本発明によれば第１に、（Ｃａ 、 Ｓ、ｒ ） （
Ｍｎ 。(Effects of the Invention) According to the present invention, firstly, (Ca, S, r) (
Mn.
Ｔｉ）Ｏ３系のペロブスカイト型構造をもつ複合酸化物
焼結体ＩＣａ Ｍｎ ０３ ｙｓｒ Ｍｎ ｏ３−ｚ
Ｃａ Ｔｉ ０３において、χを３０乃至９０モル％、
ｙをＯ乃至３０モル％、２を５乃至４０モル％の組成範
囲としたので、導電性に優れた複合酸化物焼結体を得る
ことができる。また、上記組成とすることにより遠赤外
線波長域でも高い赤外線放射率を持つ複合酸化物焼結体
を１昇ることかできる。第２に、本発明によれば上記第
１の本発明に係る複合酸化物焼結体を主成分としてセラ
ミックス発熱体を構成するので、前記複合酸化物焼結体
自体を通電加熱でき、複合酸化物焼結体から広範囲の赤
外線を直接放射さぼることができる。その結果、簡単な
構造のエネルギー効率に惨れたセラミックス発熱体を提
供することかできる。Ti) O3-based composite oxide sintered body with perovskite structure ICa Mn 03 ysr Mn o3-z
In Ca Ti 03, χ is 30 to 90 mol%,
Since y is in the composition range of O to 30 mol % and 2 is in the composition range of 5 to 40 mol %, a composite oxide sintered body with excellent conductivity can be obtained. Further, by having the above composition, it is possible to produce a composite oxide sintered body having a high infrared emissivity even in the far infrared wavelength range. Secondly, according to the present invention, since the ceramic heating element is composed mainly of the composite oxide sintered body according to the first aspect of the present invention, the composite oxide sintered body itself can be heated with electricity, and A wide range of infrared rays can be directly emitted from the sintered body. As a result, it is possible to provide a ceramic heating element with a simple structure and excellent energy efficiency.
第１図は実施例に係る原料主成分配合比及びその焼結体
の比抵抗と赤外線放射率とを示した特性表を示し、第２
図は実施例の比抵抗温度特性図を示し、第３図は実施例
の赤外線放射率の波長特性図を示す。FIG. 1 shows a characteristic table showing the blending ratio of the main components of the raw materials and the specific resistance and infrared emissivity of the sintered body according to the example.
The figure shows a resistivity temperature characteristic diagram of the example, and FIG. 3 shows a wavelength characteristic diagram of infrared emissivity of the example.
Claims (1)
カイト型構造をもつ複合酸化物焼結体において、 ｘＣａＭｎＯ＿３−ｙＳｒＭｎＯ＿３− ｚＣａＴｉＯ＿３のｘを３０乃至９０モル％、ｙを０乃
至３０モル％、ｚを５乃至４０モル％の組成範囲とした
ことを特徴とする複合酸化物焼結体。 ２、ｘＣａＭｎＯ＿３−ｙＳｒＭｎＯ＿３−ｚＣａＴｉ
Ｏ＿３のｘを３０乃至９０モル％、ｙを０乃至３０モル
％、ｚを５乃至４０モル％とした（Ｃａ、Ｓｒ）（Ｍｎ
、Ｔｉ）Ｏ＿３系のペロブスカイト型構造の導電性複合
酸化物焼結体を主成分とすることを特徴とするセラミッ
クス発熱体。[Claims] 1. In a composite oxide sintered body having a perovskite structure based on (Ca, Br) (Mn, Ti) O_3, x of xCaMnO_3-ySrMnO_3-zCaTiO_3 is 30 to 90 mol%, A composite oxide sintered body characterized by having a composition range of 0 to 30 mol% and z of 5 to 40 mol%. 2, xCaMnO_3-ySrMnO_3-zCaTi
(Ca, Sr) (Mn
, Ti)O_3-based conductive composite oxide sintered body having a perovskite structure as a main component.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61129856A JPS62288159A (en) | 1986-06-04 | 1986-06-04 | Composite oxide sintered body and ceramic heater |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61129856A JPS62288159A (en) | 1986-06-04 | 1986-06-04 | Composite oxide sintered body and ceramic heater |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62288159A true JPS62288159A (en) | 1987-12-15 |
| JPH0317785B2 JPH0317785B2 (en) | 1991-03-08 |
Family
ID=15019954
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61129856A Granted JPS62288159A (en) | 1986-06-04 | 1986-06-04 | Composite oxide sintered body and ceramic heater |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62288159A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014015388A (en) * | 2008-05-23 | 2014-01-30 | Ishihara Sangyo Kaisha Ltd | Infrared reflective material and paint, resin composition containing the same |
-
1986
- 1986-06-04 JP JP61129856A patent/JPS62288159A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014015388A (en) * | 2008-05-23 | 2014-01-30 | Ishihara Sangyo Kaisha Ltd | Infrared reflective material and paint, resin composition containing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0317785B2 (en) | 1991-03-08 |
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