JPH05129106A - Semiconductor porcelain substance - Google Patents
Semiconductor porcelain substanceInfo
- Publication number
- JPH05129106A JPH05129106A JP3314044A JP31404491A JPH05129106A JP H05129106 A JPH05129106 A JP H05129106A JP 3314044 A JP3314044 A JP 3314044A JP 31404491 A JP31404491 A JP 31404491A JP H05129106 A JPH05129106 A JP H05129106A
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- high purity
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- Compositions Of Oxide Ceramics (AREA)
- Thermistors And Varistors (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、電圧依存非直線抵抗特
性を有する半導体磁器物質に係り、特に従来品に比して
安価に提供することを可能とした磁器物質に関するもの
である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a semiconductor porcelain material having a voltage-dependent nonlinear resistance characteristic, and more particularly to a porcelain material which can be provided at a lower cost than conventional products.
【０００２】[0002]
【従来の技術】小型モータのノイズ防止用リングバリス
タに使用される半導体磁器物質は、一般にＳｒＴｉＯ3
を主成分とする系統に属する物質と、ＳｎＯ2 を主成分
とする系統の物質に分類される。後者に属するＳｎＯ2
系については、主成分であるＳｎＯ2 にＳｂ2 Ｏ5 、Ｂ
ｉ2 Ｏ3 、ＣｏＯを副成分として含有する非直線性抵抗
体に関する特許（特公昭５２−４０７６０、特公昭５２
−４７１５８）が公告され実用化されている。2. Description of the Related Art A semiconductor ceramic material used for a noise preventing ring varistor of a small motor is generally SrTiO 3
It is classified into a substance that belongs to a system whose main component is and a substance that belongs to a system whose main component is SnO 2 . SnO 2 belonging to the latter
As for the system, the main components SnO 2 to Sb 2 O 5 , B
Patents relating to non-linear resistors containing i 2 O 3 and CoO as subcomponents (Japanese Patent Publication Nos. 52-40760 and 52)
-47158) has been announced and put into practical use.
【０００３】[0003]
【発明が解決しようとする課題】上述のＳｒＴｉＯ3 を
主成分とする磁器物質においては、非直線係数αは極め
て高いという優位性を有するが、該磁器物質はその成分
に起因する焼結性の劣化により脆く、したがってモータ
に取り付ける際に割れが発生し易いなどの点で機械的強
度が小さいという欠点を有しており、特にパーツの小型
化が困難であった。The above-mentioned porcelain material containing SrTiO 3 as a main component has an advantage that the non-linear coefficient α is extremely high, but the porcelain material has a sinterability due to the component. It has a drawback that it is fragile due to deterioration and therefore has a small mechanical strength in that it is easily cracked when it is attached to a motor, and it is particularly difficult to downsize parts.
【０００４】一方、ＳｎＯ2 を主成分とする磁器物質
は、非直線係数αは前者程ではないが、実用上差し支え
のない程度の値を有する反面、焼結体の強度が前者に比
して極めて高く機械的強度が大きいため、十分前者の欠
点を償うことができるという利点を有している。しかし
ながら、ＳｎＯ2 を主成分とする磁器物質は磁器物質の
原料にＳｎＯ2 、Ｓｂ2 Ｏ5 、Ｂｉ2 Ｏ3 およびＣｏＯ
などといった高価な粉末を使用するため、製品の価格が
非常に高くなってしまうという問題点があった。また、
ＳｎＯ2 を主成分とする磁器物質は、ＳｒＴｉＯ3 を主
成分とする磁器物質ほどの高い非直線係数を得ることが
できないため、改善が要求されている。On the other hand, although the non-linear coefficient α of the porcelain material containing SnO 2 as a main component is not as large as that of the former, the strength of the sintered body is higher than that of the former, while it has a value that is practically acceptable. Since it is extremely high and has high mechanical strength, it has an advantage that the former drawback can be sufficiently compensated. However, the porcelain material containing SnO 2 as a main component is not limited to SnO 2 , Sb 2 O 5 , Bi 2 O 3 and CoO.
Since expensive powder such as the above is used, the price of the product becomes very high. Also,
Since the porcelain material containing SnO 2 as a main component cannot obtain a higher nonlinear coefficient than that of the porcelain material containing SrTiO 3 as a main component, improvement is required.
【０００５】そこで、本発明は上記従来の技術の問題点
を解決し、従来のＳｎＯ2 を主成分とする磁器物質と同
程度以上の非直線係数および機械的強度を有し、安価な
コストで製造することができる半導体磁器物質を提供す
ることを目的とする。Therefore, the present invention solves the above-mentioned problems of the prior art, has a non-linear coefficient and mechanical strength that are equal to or higher than those of the conventional porcelain having SnO 2 as a main component, and is inexpensive. An object is to provide a semiconductor porcelain material that can be manufactured.
【０００６】[0006]
【課題を解決するための手段】本発明者等は、上記課題
を解決するため鋭意研究した結果、主成分としてＳｎＯ
2 、ＺｎＯ、Ｓｂ2 Ｏ5 およびＢｉ2 Ｏ3 を、それぞれ
20〜99モル％、 0.5〜70モル％、0.05〜25モル％および
0.05〜15モル％の範囲で各成分の合計が 100モル％とな
るように配合し、これにＰｂ、Ｇｅ、Ｓｉ、Ｍｎ、Ｆｅ
およびＮｉの各酸化物からなる群より選ばれる少なくと
も１種類以上を0.05〜10重量％添加することにより、上
記目的が達成されることを見い出し、本発明を提供する
ことができた。Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that SnO as a main component.
2 , ZnO, Sb 2 O 5 and Bi 2 O 3 are respectively
20-99 mol%, 0.5-70 mol%, 0.05-25 mol% and
It is blended so that the total of each component becomes 100 mol% in the range of 0.05 to 15 mol%, and Pb, Ge, Si, Mn, Fe are added to this.
It was found that the above object can be achieved by adding 0.05 to 10% by weight of at least one selected from the group consisting of and oxides of Ni, and the present invention can be provided.
【０００７】すなわち、本発明は、ＳｎＯ2 20〜99モル
％、ＺｎＯ 0.5〜70モル％、Ｓｂ2 Ｏ5 0.05〜25モル％
およびＢｉ2 Ｏ3 0.05〜15モル％からなり、その合計が
100モル％となる各成分を主成分として構成され、上記
主成分のほかにＰｂ、Ｇｅ、Ｓｉ、Ｍｎ、ＦｅおよびＮ
ｉの各酸化物からなる群より選ばれる少なくとも１種類
以上が主成分の合計重量に対し0.05〜10重量％添加され
ていることを特徴とする半導体磁器物質を提供するもの
である。That is, according to the present invention, SnO 2 is 20 to 99 mol%, ZnO is 0.5 to 70 mol%, Sb 2 O 5 is 0.05 to 25 mol%.
And Bi 2 O 3 0.05 to 15 mol%, the total of which is
The main component is 100 mol% of each component. In addition to the above main components, Pb, Ge, Si, Mn, Fe and N
At least one selected from the group consisting of the oxides of i is added in an amount of 0.05 to 10% by weight based on the total weight of the main components.
【０００８】[0008]
【作用】ＳｎＯ2 を主成分とする磁器物質のＳｎＯ2 の
一部または相当部分をＺｎＯに代えても非直線抵抗値α
および抗折強度τ（kg／cm2 ）は同等以上であることを
確認できたため、高価なＳｎＯ2 粉末を安価なＺｎＯに
代替えすることにより、製造コストの低減化を可能にし
たが、さらにＰｂ、Ｇｅ、Ｓｉ、Ｍｎ、ＦｅおよびＮｉ
の各金属酸化物のうち、少なくとも一種類以上を主成分
の合計重量に対し0.05〜10重量％含有させることによ
り、磁器物質の非直線係数値αが向上することを見出し
本発明に到達した。The non-linear resistance value α is obtained even if a part of SnO 2 of the porcelain material containing SnO 2 as a main component or a corresponding part is replaced with ZnO.
Since it was confirmed that the bending strength τ (kg / cm 2 ) was equal or higher, the manufacturing cost could be reduced by replacing the expensive SnO 2 powder with inexpensive ZnO. , Ge, Si, Mn, Fe and Ni
The inventors have found that the non-linear coefficient value α of a porcelain substance is improved by containing at least one of these metal oxides in an amount of 0.05 to 10 wt% with respect to the total weight of the main components, and arrived at the present invention.
【０００９】以下、実施例により本発明をさらに詳細に
説明する。しかし本発明の範囲は以下の実施例により制
限されるものではない。Hereinafter, the present invention will be described in more detail with reference to examples. However, the scope of the present invention is not limited by the following examples.
【００１０】[0010]
【実施例】本実施例では、以下に示す要領で本発明の半
導体磁器物質（バリスタ）を作製し（原料および配合量
は表１ないし５に記載）、それぞれの半導体磁器物質
（バリスタ）のバリスタ電圧、非直線係数値αおよび機
械的強度を測定し、その結果を表１ないし５に示した。
なお、比較例として上記同様の成分を用い、本発明の範
囲から外れる配合量で配合して半導体磁器物質（バリス
タ）を作製し、それらについてバリスタ電圧、非直線係
数αおよび機械的強度を測定し、その結果を表１ないし
５に併記した（比較例は表１ないし５の試料番号欄に＊
を付した）。EXAMPLES In this example, semiconductor porcelain materials (varistors) of the present invention were manufactured in the following manner (raw materials and compounding amounts are shown in Tables 1 to 5), and varistor of each semiconductor porcelain material (varistor). The voltage, the non-linear coefficient value α and the mechanical strength were measured, and the results are shown in Tables 1 to 5.
As comparative examples, the same components as described above were used, and compounded in a compounding amount outside the scope of the present invention to prepare semiconductor porcelain materials (varistor), and varistor voltage, non-linear coefficient α and mechanical strength of them were measured. The results are also shown in Tables 1 to 5 (for comparative examples, in the sample number column of Tables 1 to 5, *
Attached).
【００１１】まず、高純度ＳｎＯ2 、ＺｎＯ、Ｓｂ2 Ｏ
5 およびＢｉ2 Ｏ3 を所定量ずつ秤量配合したものをボ
ールミルにて１０時間湿式撹拌を行い、乾燥および粉砕
した後大気中において 1,100℃で２時間仮焼した。仮焼
後、得られた焼結体を再び粉砕し、これを主成分原料粉
末とした。次いで、該主成分原料粉末にＰｂ、Ｇｅ、Ｓ
ｉ、Ｍｎ、ＦｅおよびＮｉの各金属酸化物のうち、少な
くとも一種類以上を所定量秤量配合し、ボールミルにて
１０時間湿式撹拌を行い、乾燥した。First, high-purity SnO 2 , ZnO, Sb 2 O
5 and Bi 2 O 3 were weighed and mixed in predetermined amounts, wet-stirred in a ball mill for 10 hours, dried and pulverized, and then calcined in the atmosphere at 1,100 ° C. for 2 hours. After calcination, the obtained sintered body was pulverized again, and this was used as a main component raw material powder. Next, Pb, Ge, S is added to the main component raw material powder.
At least one kind of each of metal oxides of i, Mn, Fe, and Ni was weighed and mixed in a predetermined amount, wet-stirred for 10 hours in a ball mill, and dried.
【００１２】次に、この混合粉末に10〜15重量％のポリ
ビニールアルコールを有機結合剤として混合して造粒
し、約１ton/cm2 の圧力で圧縮し、直径10mm、厚さ1.0m
m の円板に成形した。成形後、この円板を大気中におい
て 1,360〜1,420 ℃で４時間焼成して磁器試料を得、そ
の表裏主面に銀ペーストを塗布して 800℃で焼き付け、
銀電極を形成した。Next, 10 to 15% by weight of polyvinyl alcohol was mixed as an organic binder into the mixed powder, and the mixture was granulated and compressed at a pressure of about 1 ton / cm 2 to have a diameter of 10 mm and a thickness of 1.0 m.
It was formed into a disk of m. After molding, this disc was fired in the atmosphere at 1,360 to 1,420 ° C for 4 hours to obtain a porcelain sample. Silver paste was applied to the front and back main surfaces and baked at 800 ° C.
A silver electrode was formed.
【００１３】上記のようにして作製した試料について、
それぞれバリスタ電圧Ｖ1 、非直線係数αおよび抗折強
度τ（kg／cm2 ）を測定した。なお、バリスタ電圧
Ｖ1 、非直線係数αおよび抗折強度τ（kg／cm2 ）は以
下のようにして測定した。With respect to the sample manufactured as described above,
The varistor voltage V 1 , the non-linear coefficient α and the bending strength τ (kg / cm 2 ) were measured, respectively. The varistor voltage V 1 , the non-linear coefficient α and the bending strength τ (kg / cm 2 ) were measured as follows.
【００１４】(1) バリスタ電圧Ｖ1 の測定法 試料の接点に直流定電流電源および直流電流計を直列に
接続する。また、試料の接点の両端に直流電圧計を並列
に接続して、直流定電流電源より試料に１mAの電流を流
すために要する電圧を直流電圧計で測定してバリスタ電
圧Ｖ1(V) とした。(1) Method for measuring varistor voltage V 1 A DC constant current power supply and a DC ammeter are connected in series to the contact of the sample. Also, a DC voltmeter was connected in parallel to both ends of the contact of the sample, and the voltage required to flow a current of 1 mA from the DC constant current power supply to the sample was measured with the DC voltmeter to obtain the varistor voltage V 1 (V).
【００１５】(2) 非直線係数αの測定法 １mAの電流を流すのに要する電圧Ｖ1 および10mAの電流
を流すのに要する電圧Ｖ10を測定して、各々の測定値を
次式に代入して非直線係数αを算出する。 α＝１／log （Ｖ10／Ｖ1 ）(2) Method for measuring non-linear coefficient α Measure voltage V 1 required to pass a current of 1 mA and voltage V 10 required to pass a current of 10 mA, and substitute each measured value into the following equation. Then, the nonlinear coefficient α is calculated. α = 1 / log (V 10 / V 1 )
【００１６】(3) 抗折強度τ（kg／cm2 ）の測定法 一般に脆性物質の機械的強度の目安として抗折強度が用
いられるため、試料の抗折強度を測定した。(3) Method of measuring bending strength τ (kg / cm 2 ) Since bending strength is generally used as a measure of the mechanical strength of brittle substances, the bending strength of the sample was measured.
【００１７】幅ｗcm、厚さｔcmの方形断面を有する試料
を上述の円板試料の作製過程において同時に作製し、磁
器試料（銀ペースト塗布、焼き付けは行わず）を用意し
た。この試料を支点間距離ｌcmの２つの支点上に水平に
置き、中央部に毎秒約５kgの速さで荷重を加え、最大破
壊荷重Ｐｍを測定し、次式により抗折強度を算出した。 τ＝ 3／2 ×Ｐｍｌ／ｗｔ2 kg/cm2 A sample having a rectangular cross section with a width of wcm and a thickness of tcm was prepared at the same time in the process of preparing the above-mentioned disc sample to prepare a porcelain sample (no silver paste coating or baking). This sample was placed horizontally on two fulcrums with a fulcrum distance of 1 cm, a load was applied to the central portion at a speed of about 5 kg per second, the maximum breaking load Pm was measured, and the bending strength was calculated by the following formula. τ = 3/2 × Pml / wt 2 kg / cm 2
【００１８】[0018]
【表１】 [Table 1]
【表２】 [Table 2]
【表３】 [Table 3]
【表４】 [Table 4]
【表５】 [Table 5]
【００１９】表１ないし５からもわかるように、本発明
品はバリスタ電圧、非直線係数値αおよび抗折強度τが
総合的に優れているが、比較例として併記した本発明の
範囲から外れるものについては、高い抗折強度τを有し
ていても非直線係数値αが低いなど総合的に優れている
ものはなかった。As can be seen from Tables 1 to 5, the varistor voltage, the non-linear coefficient value α and the bending strength τ of the present invention are totally excellent, but they are out of the range of the present invention described as a comparative example. Among them, none of them had a high bending strength τ and were excellent overall, such as a low nonlinear coefficient value α.
【００２０】[0020]
【発明の効果】本発明の半導体磁器物質の開発により、
高価なＳｎＯ2 粉末を安価なＺｎＯに代替えすることが
できるようになったため、従来のＳｎＯ2 を主成分とす
る半導体磁器物質と同等以上の非直線係数および機械的
強度を有するものを低価格で提供することができるよう
になった。By the development of the semiconductor porcelain material of the present invention,
Since it has become possible to replace expensive SnO 2 powder with inexpensive ZnO, it is possible to use a material having a non-linear coefficient and mechanical strength equal to or higher than that of a conventional semiconductor ceramic material containing SnO 2 as a main component at a low price. It is now possible to provide.
Claims (1)
モル％、Ｓｂ2 Ｏ5 0.05〜25モル％およびＢｉ2 Ｏ3 0.
05〜15モル％からなり、その合計が 100モル％となる各
成分を主成分として構成され、上記主成分のほかにＰ
ｂ、Ｇｅ、Ｓｉ、Ｍｎ、ＦｅおよびＮｉの各酸化物から
なる群より選ばれる少なくとも１種類以上が主成分の合
計重量に対し0.05〜10重量％添加されていることを特徴
とする半導体磁器物質。1. SnO 2 20-99 mol%, ZnO 0.5-70
Mol%, Sb 2 O 5 0.05-25 mol% and Bi 2 O 3 0.
It is composed of 05 to 15 mol% and each of the components is 100 mol% in total.
At least one selected from the group consisting of oxides of b, Ge, Si, Mn, Fe and Ni is added in an amount of 0.05 to 10% by weight based on the total weight of the main components. ..
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3314044A JPH05129106A (en) | 1991-10-31 | 1991-10-31 | Semiconductor porcelain substance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3314044A JPH05129106A (en) | 1991-10-31 | 1991-10-31 | Semiconductor porcelain substance |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05129106A true JPH05129106A (en) | 1993-05-25 |
Family
ID=18048543
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3314044A Withdrawn JPH05129106A (en) | 1991-10-31 | 1991-10-31 | Semiconductor porcelain substance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05129106A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1683880A2 (en) | 2005-01-24 | 2006-07-26 | Areva T&D Sa | Method for preparing semiconducting ceramics, made of metal oxides, preferably tin oxide, used particularly for varistors. |
| WO2007128785A1 (en) * | 2006-05-05 | 2007-11-15 | Areva T&D Sa | Use of b203 in a tin oxide-based semi conductive ceramic for reducing the leakage current thereof and for possibly stabilizing the electrical properties thereof |
-
1991
- 1991-10-31 JP JP3314044A patent/JPH05129106A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1683880A2 (en) | 2005-01-24 | 2006-07-26 | Areva T&D Sa | Method for preparing semiconducting ceramics, made of metal oxides, preferably tin oxide, used particularly for varistors. |
| WO2007128785A1 (en) * | 2006-05-05 | 2007-11-15 | Areva T&D Sa | Use of b203 in a tin oxide-based semi conductive ceramic for reducing the leakage current thereof and for possibly stabilizing the electrical properties thereof |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A300 | Withdrawal of application because of no request for examination |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 19990107 |