JPH08255703A - Method for manufacturing barium titanate-based semiconductor porcelain - Google Patents
Method for manufacturing barium titanate-based semiconductor porcelainInfo
- Publication number
- JPH08255703A JPH08255703A JP7029930A JP2993095A JPH08255703A JP H08255703 A JPH08255703 A JP H08255703A JP 7029930 A JP7029930 A JP 7029930A JP 2993095 A JP2993095 A JP 2993095A JP H08255703 A JPH08255703 A JP H08255703A
- Authority
- JP
- Japan
- Prior art keywords
- porcelain
- pulverization
- barium titanate
- raw material
- calcination
- 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
- 229910052573 porcelain Inorganic materials 0.000 title claims abstract description 56
- 239000004065 semiconductor Substances 0.000 title claims abstract description 29
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910002113 barium titanate Inorganic materials 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims description 21
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000000843 powder Substances 0.000 claims abstract description 47
- 238000010298 pulverizing process Methods 0.000 claims abstract description 47
- 239000000203 mixture Substances 0.000 claims abstract description 27
- 239000002994 raw material Substances 0.000 claims abstract description 21
- 238000001354 calcination Methods 0.000 claims abstract description 20
- 238000010304 firing Methods 0.000 claims abstract description 13
- 238000005245 sintering Methods 0.000 claims abstract description 3
- 239000006104 solid solution Substances 0.000 abstract description 18
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 2
- 239000002245 particle Substances 0.000 description 15
- 239000007858 starting material Substances 0.000 description 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- 239000000919 ceramic Substances 0.000 description 7
- 239000011572 manganese Substances 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- 229910052745 lead Inorganic materials 0.000 description 6
- 229910052727 yttrium Inorganic materials 0.000 description 6
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910018380 Mn(NO3)2.6H2 O Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000005036 potential barrier Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Thermistors And Varistors (AREA)
Abstract
(57)【要約】
【目的】 仮焼により得られる半導体化剤含有チタン酸
バリウム系固溶体粉末について、焼成前に行う粉砕処理
の程度を制御することにより、電気特性の優れた半導体
磁器を得る。特定組成比率範囲内においてその効果は特
に顕著である。
【構成】 焼結に供する際の原料粉体の比表面積と、粉
砕前仮焼直後の原料粉体の比表面積との比が、焼成直前
／仮焼直後の値として、１．２以上２．５以下の範囲内
に入るように、原料粉体を粉砕する。(57) [Summary] [Objective] A semiconductor porcelain having excellent electrical properties is obtained by controlling the degree of pulverization treatment performed before firing for barium titanate-based solid solution powder containing a semiconducting agent obtained by calcination. The effect is particularly remarkable in the specific composition ratio range. [Structure] The ratio of the specific surface area of the raw material powder to be subjected to sintering and the specific surface area of the raw material powder immediately after calcination before pulverization is 1.2 or more as a value immediately before firing / immediately after calcination. The raw material powder is pulverized so as to fall within the range of 5 or less.
Description
【０００１】[0001]
【産業上の利用分野】本発明は、正の抵抗温度特性を有
するチタン酸バリウム系半導体磁器の製造方法に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a barium titanate based semiconductor ceramic having a positive resistance temperature characteristic.
【０００２】[0002]
【従来の技術】チタン酸バリウムに、微量の稀土類元
素、あるいは、ニオブ、タンタル、ビスマス、アンチモ
ン、タングステンなどの元素を添加することにより、正
の抵抗温度特性を有する半導体磁器が得られることが知
られている。さらに、マンガンを微量添加することによ
り、抵抗温度特性における抵抗温度係数を上昇させるこ
とができることも知られている。2. Description of the Related Art A semiconductor ceramic having a positive resistance temperature characteristic can be obtained by adding a trace amount of a rare earth element or elements such as niobium, tantalum, bismuth, antimony and tungsten to barium titanate. Are known. It is also known that the resistance temperature coefficient in the resistance temperature characteristic can be increased by adding a small amount of manganese.
【０００３】また、この正の抵抗温度特性は、結晶粒界
のポテンシャル障壁に起因するものとされており、急峻
な正の抵抗温度特性を発現させるために、一般にＳｉＯ
2 などを添加して、マンガンの結晶内部への固溶をでき
るだけ抑えるようにすることも知られている。Further, this positive resistance temperature characteristic is attributed to the potential barrier of the crystal grain boundary, and in order to develop a steep positive resistance temperature characteristic, SiO is generally used.
It is also known to add 2 or the like to suppress the solid solution of manganese in the crystal as much as possible.
【０００４】このような正の抵抗温度特性を有する半導
体磁器は、電流制限、温度検知、定温度発熱体などに使
用されているが、一般に、電流制限の用途に用いられる
チタン酸バリウム系半導体磁器の特性としては、室温で
の比抵抗〔ρ〕が小さいこと、耐電圧〔Ｖ〕が高いこ
と、抵抗温度係数〔α〕が大きいことなどがあげられ
る。このような電流制限用の半導体磁器の特性として
は、低抵抗で、小型軽薄化の素子を得るために、室温比
抵抗が小さく、かつ、耐電圧が高いものが要求されてい
る。The semiconductor porcelain having such a positive resistance temperature characteristic is used for current limitation, temperature detection, constant temperature heating element and the like. Generally, barium titanate type semiconductor porcelain used for current limitation applications. The characteristics of 1 are that the specific resistance [ρ] at room temperature is small, the withstand voltage [V] is high, and the temperature coefficient of resistance [α] is large. As characteristics of such a current-limiting semiconductor ceramic, it is required to have a low resistance at room temperature and a high withstand voltage in order to obtain a small-sized and light-weight element.
【０００５】この要求を満たすべく、比抵抗−耐電圧特
性を向上させるために、チタン酸バリウム系半導体磁器
組成物におけるチタン酸バリウムのＢａの一部を、キュ
リー点シフターであるＳｒやＰｂで同時に置換したもの
が、特開昭５３−９８０９５号公報に、また、ＳｒやＰ
ｂで置換すると共にＣａを含有させたものが、特公昭６
３−２８３２４号公報に、それぞれ開示されている。上
記公報によれば、出発原料として、磁器構成成分の酸化
物または炭酸塩を所定の割合で配合して湿式混合した
後、仮焼してチタン酸バリウム系固溶体粉末を得、これ
を粉砕し、造粒、成形、焼成して、チタン酸バリウム系
半導体磁器を得ている。In order to meet this requirement, in order to improve the specific resistance-withstand voltage characteristics, a part of Ba of barium titanate in the barium titanate-based semiconductor ceramic composition is simultaneously treated with Curie point shifters Sr and Pb. The substituted one is disclosed in JP-A-53-98095, and Sr and P
The one which is substituted with b and contains Ca is disclosed in JP-B-6.
Each of which is disclosed in JP-A-3-28324. According to the above-mentioned publication, as a starting material, oxides or carbonates of porcelain constituents are blended in a predetermined ratio and wet-mixed, and then calcined to obtain barium titanate-based solid solution powder, which is crushed, The barium titanate-based semiconductor porcelain is obtained by granulating, molding and firing.
【０００６】また、焼結体を均一かつ微細化するため
に、仮焼して得られたチタン酸バリウム系固溶体粉末の
粒径を１．０〜３．０μｍにしたものを用いることもな
されている（特開平１−２２００１号公報）。さらに、
液相溶液反応により合成されたチタン酸バリウム系組成
物を利用することも知られている（特開平３−５４１６
５号公報）。Further, in order to make the sintered body uniform and fine, it is also possible to use a barium titanate-based solid solution powder having a particle size of 1.0 to 3.0 μm obtained by calcination. (Japanese Patent Laid-Open No. 1-2001). further,
It is also known to utilize a barium titanate-based composition synthesized by a liquid phase solution reaction (Japanese Patent Laid-Open No. 3-5416).
No. 5).
【０００７】[0007]
【発明が解決しようとする課題】上述した従来方法で
は、焼結体の粒径の微細化などによる比抵抗−耐電圧特
性の改善に重点がおかれており、耐電圧と室温比抵抗の
比が１０以上のものも得られている。しかしながら、こ
のようなものについては、抵抗温度係数の値について
は、特に明記されていないのが現状である。本発明者ら
の追試によれば、たとえば、比抵抗１０Ωｃｍで１０％
／℃、比抵抗２０Ωｃｍで１４％／℃程度の値しか得ら
れず、優れた特性とはいえない。また、原料粉体として
液相溶液反応により合成されたチタン酸バリウム系組成
物を利用することは、コスト面において不利である。In the above-mentioned conventional method, the emphasis is placed on the improvement of the specific resistance-withstand voltage characteristic by making the grain size of the sintered body finer, and the ratio of the withstand voltage and the room temperature specific resistance is emphasized. Those having a value of 10 or more are also obtained. However, regarding such a material, the value of the temperature coefficient of resistance is not specified in the present situation. According to an additional test by the present inventors, for example, a specific resistance of 10 Ωcm is 10%.
/ ° C., specific resistance of 20 Ωcm, only about 14% / ° C. is obtained, which is not an excellent characteristic. In addition, it is disadvantageous in terms of cost to use the barium titanate-based composition synthesized by the liquid phase solution reaction as the raw material powder.
【０００８】[0008]
【課題を解決するための手段】本発明は、一般的な固相
法で製造した粉体を用いて作成したチタン酸バリウム系
半導体磁器において、比抵抗−耐電圧特性が良好で、か
つ、抵抗温度係数の大きい半導体磁器を提供するもので
ある。The present invention provides a barium titanate-based semiconductor porcelain prepared by using a powder produced by a general solid phase method, which has good resistivity-withstand voltage characteristics and resistance. A semiconductor porcelain having a large temperature coefficient is provided.
【０００９】本発明者らは、従来方法では、仮焼して得
られる半導体化剤含有チタン酸バリウム系固溶体粉末
（磁器原料粉末）が、焼成前に一般的に行われている粉
砕において、過度な粉砕によって新たに生成する反応活
性な界面や微粉体の比率が高くなるため、特性改善用添
加剤であるＭｎの結晶内部への固溶が進行してしまう、
と想定し、上記磁器原料粉体の粉砕の度合いを制御する
ことにより、比抵抗−耐電圧特性が良好で、しかも抵抗
温度係数の大きい半導体磁器を得、本発明に到達した。According to the conventional method, the present inventors have found that the semiconducting agent-containing barium titanate-based solid solution powder (porcelain raw material powder) obtained by calcination is excessively crushed during pulverization which is generally performed before firing. Since the ratio of the reaction-active interface and fine powder newly generated by the fine pulverization increases, the solid solution of Mn, which is an additive for property improvement, inside the crystal proceeds.
By controlling the degree of pulverization of the above porcelain raw material powder, a semiconductor porcelain having a good specific resistance-withstand voltage characteristic and a large temperature coefficient of resistance was obtained, and the present invention was reached.
【００１０】すなわち本発明は、磁器焼成に用いる原料
粉体に関し、焼結に供する際の原料粉体の比表面積と、
粉砕前仮焼直後の原料粉体の比表面積との比（以下、こ
れを「粉砕度」と定義する）が、焼成直前／仮焼直後の
値として、１．２以上２．５以下の範囲内に入るよう
に、仮焼後の原料粉体を粉砕することを特徴とするチタ
ン酸バリウム系半導体磁器の製造方法である。That is, the present invention relates to a raw material powder used for porcelain firing, and a specific surface area of the raw material powder when it is subjected to sintering,
The ratio with the specific surface area of the raw material powder immediately after calcination before pulverization (hereinafter, this is defined as "pulverization degree") is in the range of 1.2 or more and 2.5 or less as the value immediately before firing / immediately after calcination. It is a method for manufacturing a barium titanate-based semiconductor porcelain, characterized in that the raw material powder after calcination is crushed so as to enter inside.
【００１１】本発明方法を適用することにより、特に下
記の半導体磁器組成において優れた特性、具体的には、
室温比抵抗が３０Ωｃｍ以下で、耐電圧と室温比抵抗の
比が１０以上であるとともに、抵抗温度係数と室温比抵
抗の対数値との比が１２以上である、という特性を有す
る磁器が得られる。By applying the method of the present invention, particularly excellent characteristics in the following semiconductor porcelain composition, specifically,
A porcelain having characteristics that the room temperature specific resistance is 30 Ωcm or less, the ratio of withstand voltage to room temperature specific resistance is 10 or more, and the ratio of the temperature coefficient of resistance to the logarithmic value of room temperature specific resistance is 12 or more is obtained. .
【００１２】磁器組成が（Ｂａ1-x-y-z Ｓｒx Ｐｂy Ｙ
z ) A ＴｉB Ｏ3 ＋αＳｉＯ2 ＋βＭｎで表され、ｘ，
ｙ，ｚ，Ａ，Ｂ，α，βはそれぞれ、 ０．１２ ≦ ｘ ≦ ０．３３ ０．１２ ≦ ｙ ≦ ０．３３ ０．２５ ≦ ｘ＋ｙ ≦ ０．４５ ０．００２ ≦ ｚ ≦ ０．００４５ ０．９９５ ≦ Ａ／Ｂ ≦ １．００５ ０．０１５ ≦ α ≦ ０．０２５ ０．１０ ≦ β／ｚ ≦ ０．２０ の範囲内にある半導体磁器組成物。[0012] The ceramic composition is (Ba 1-xyz Sr x Pb y Y
z ) A Ti B O 3 + αSiO 2 + βMn, x,
y, z, A, B, α, β are respectively 0.12 ≤ x ≤ 0.33 0.12 ≤ y ≤ 0.33 0.25 ≤ x + y ≤ 0.45 0.002 ≤ z ≤ 0.0045 A semiconductor ceramic composition in the range of 0.995 ≤ A / B ≤ 1.005 0.015 ≤ α ≤ 0.025 0.10 ≤ β / z ≤ 0.20.
【００１３】本発明方法において、使用する磁器原料粉
体の特徴を表現する場合に、比表面積などの具体的数値
を用いず、「粉砕度」という比率を用いた理由は、磁器
原料であるチタン酸バリウム系固溶体粉末は仮焼によっ
てしか得られず、そしてその固溶体粉末をそのまま磁器
に焼成しても望ましい特性が全く得られないためと、仮
焼によって得られる固溶体粉末は、各出発原料粉体の粒
径や種類などにより最適仮焼温度が異なるので、結果と
して得られる固溶体粉末の粒度分布が変化するため、固
定した数値を用いることができないからである。In the method of the present invention, when the characteristics of the porcelain raw material powder to be used are expressed, the ratio of "pulverization degree" is used without using specific numerical values such as specific surface area. The barium acid-based solid solution powder can be obtained only by calcination, and even if the solid solution powder is directly baked into porcelain, desired characteristics cannot be obtained at all. This is because the optimum calcination temperature varies depending on the particle size, type, etc., and the particle size distribution of the resulting solid solution powder changes, so a fixed numerical value cannot be used.
【００１４】以下、本発明について、具体的に述べる。
本発明において用いる出発原料としては、通常、各成分
元素の酸化物または炭酸塩を用いるが、仮焼の過程で酸
化物の形態に変化するものであれば、特にこれらに限定
されるものではない。イットリウムやマンガンなどの、
添加量がわずかである成分については、磁器組成物への
均一分散の面から、硝酸塩の水溶液として添加するのが
好適である。The present invention will be specifically described below.
As the starting material used in the present invention, an oxide or carbonate of each component element is usually used, but it is not particularly limited as long as it changes into an oxide form in the process of calcination. . Such as yttrium and manganese,
It is preferable to add the component added in a small amount as an aqueous solution of nitrate from the viewpoint of uniform dispersion in the porcelain composition.
【００１５】出発原料として用いる物質が粉体である場
合、通常、その粒径は小さい方が磁器焼結体の粒径（グ
レイン）も小さくなるため好ましい。たとえば、出発原
料として酸化チタンを用いる際には、粒径の小さいルチ
ル型結晶のものが好ましく、その粒径としては、１μｍ
以下のものが好適に使用できる。When the substance used as the starting material is a powder, it is usually preferable that the particle size is smaller because the particle size (grain) of the porcelain sintered body is also smaller. For example, when titanium oxide is used as a starting material, rutile type crystals having a small particle size are preferable, and the particle size is 1 μm.
The following can be preferably used.
【００１６】これら出発原料は、ボールミルなどの手法
により、十分に湿式混合を行った後、脱水乾燥する。乾
燥後の混合粉体は、その組成によっても異なるが、１０
００〜１１５０℃の間の温度で仮焼される。仮焼温度が
１０００℃以下の場合には、各成分の固溶が十分に進ま
ず、また、仮焼温度が１１５０℃以上の場合には、仮焼
後の粉末において、粒子間の融着が激しいために、粉砕
度合いの制御が困難となるからである。These starting materials are thoroughly wet-mixed by a method such as a ball mill and then dehydrated and dried. The mixed powder after drying varies depending on its composition, but is 10
It is calcined at a temperature between 00 and 1150 ° C. When the calcination temperature is 1000 ° C. or lower, the solid solution of each component does not proceed sufficiently, and when the calcination temperature is 1150 ° C. or higher, fusion between particles is caused in the powder after calcination. This is because it is difficult to control the degree of pulverization because it is violent.
【００１７】このようにして得られたチタン酸バリウム
系固溶体粉末は、乾式で解砕を行った後、湿式粉砕す
る。この一連の粉砕操作の際、粉砕度が１．２以上２．
５以下となるように条件設定を行う。粉砕度が２．５以
上の場合には、粒度分布が幅広くなってしまうので、焼
結体の粒径分布が悪くなり、その結果として、耐電圧と
室温比抵抗の比が１０以上のものが得られない。また、
粉砕度が１．２以下の場合には、粉砕が不十分になるの
で、スラリー中の固溶体粉末の分散が困難となり、次い
で行う造粒により得られる顆粒の充填性が悪く、十分な
焼結密度が得られない。The barium titanate solid solution powder thus obtained is crushed by a dry method and then wet crushed. During this series of pulverization operations, the degree of pulverization is 1.2 or more.2.
The condition is set so that it is 5 or less. When the pulverization degree is 2.5 or more, the particle size distribution becomes broad, so that the particle size distribution of the sintered body is deteriorated, and as a result, the ratio of withstand voltage to room temperature specific resistance is 10 or more. I can't get it. Also,
When the pulverization degree is 1.2 or less, the pulverization becomes insufficient, so that it becomes difficult to disperse the solid solution powder in the slurry, the packing property of the granules obtained by the subsequent granulation is poor, and the sufficient sinter density is obtained. Can't get
【００１８】上記湿式粉砕には、通常、ボールミルを用
いるが、その際の粉砕度制御のための条件設定について
は、粉砕メディアの材質（ジルコニアやテフロンなど）
や大きさ、粉砕時間などで調節する。また、固溶体粉末
の粉砕度が１．２以上２．５以下の範囲に入るように条
件設定できるのであれば、サンドグラインドミルなどの
他の粉砕手法も採用可能である。A ball mill is usually used for the above-mentioned wet pulverization, and the condition for controlling the pulverization degree at that time is set by the material of the pulverizing media (zirconia, Teflon, etc.).
Adjust the size, size, and crushing time. Further, if the conditions can be set so that the pulverization degree of the solid solution powder falls within the range of 1.2 or more and 2.5 or less, other pulverization methods such as a sand grind mill can be adopted.
【００１９】なお、粉砕度の算出には、ＢＥＴ比表面積
を使用する。適切な粉砕度となった湿式粉砕後の固溶体
粉末スラリーは、バインダを添加し、造粒、成形後、焼
成し、焼結体磁器とする。The BET specific surface area is used to calculate the pulverization degree. The wet-pulverized solid solution powder slurry having an appropriate degree of pulverization is added with a binder, granulated, molded, and fired to obtain a sintered body porcelain.
【００２０】次に、半導体磁器の組成について説明す
る。ＳｒやＰｂを含有させると、チタン酸バリウムのＢ
ａサイトと置換し、耐電圧特性や抵抗温度係数が改善さ
れる。その適切な範囲はそれぞれ、チタン酸バリウムの
Ｔｉ原子に対し、Ｓｒ（ｘ）、Ｐｂ（ｙ）ともに１２原
子％以上で、かつ、これらの和が２５原子％以上であ
る。ＳｒまたはＰｂのどちらかの置換量が１２原子％未
満であったり、ＳｒとＰｂの置換量の和が２５原子％未
満である場合には、得られる焼結体の粒径が小さくなり
にくく、比抵抗−耐電圧特性あるいは比抵抗−抵抗温度
係数特性の劣った磁器しか得られなくなる。また、Ｓｒ
およびＰｂの置換量の和が４５モル％を越えると、室温
比抵抗が３０Ωｃｍを越えてしまい、好ましくない。Next, the composition of the semiconductor ceramic will be described. When Sr or Pb is contained, B of barium titanate is added.
By substituting the a site, the withstand voltage characteristic and the temperature coefficient of resistance are improved. The appropriate range is 12 atom% or more of both Sr (x) and Pb (y) with respect to the Ti atom of barium titanate, and the sum of these is 25 atom% or more. When the substitution amount of either Sr or Pb is less than 12 atom%, or when the sum of the substitution amounts of Sr and Pb is less than 25 atom%, it is difficult to reduce the particle size of the obtained sintered body, Only porcelain having inferior specific resistance-withstand voltage characteristics or specific resistance-resistance temperature coefficient characteristics can be obtained. Also, Sr
If the sum of the substitution amounts of Pb and Pb exceeds 45 mol%, the room temperature resistivity exceeds 30 Ωcm, which is not preferable.
【００２１】さらに、半導体磁器組成物におけるチタン
酸バリウム部分、すなわち（Ｂａ1-x-y-z Ｓｒx Ｐｂy
Ｙz ) A ＴｉB Ｏ3 でのＡサイト構成成分とＢサイト構
成成分、の原子比（Ａ／Ｂ値）は、０．９９５以上１．
００５以下が好ましい。Ａ／Ｂ値が０．９９５未満の場
合には、室温比抵抗が３０Ωｃｍを越えてしまうため好
ましくなく、Ａ／Ｂ値が１．００５を越えると、比抵抗
−耐電圧特性が低下する。Further, the barium titanate portion in the semiconductor porcelain composition, that is, (Ba 1-xyz Sr x Pby )
The atomic ratio (A / B value) of the A site constituent component and the B site constituent component in Y z ) A Ti B O 3 is 0.995 or more.
It is preferably 005 or less. When the A / B value is less than 0.995, the room temperature specific resistance exceeds 30 Ωcm, which is not preferable, and when the A / B value exceeds 1.005, the specific resistance-withstand voltage characteristic deteriorates.
【００２２】半導体化剤であるイットリウムの添加量
（ｚ）については、チタン酸バリウムのＴｉ原子量に対
し、０．２原子％以上０．４５原子％以下が好ましい。
イットリウムの添加量が、０．２原子％未満の場合に
は、比抵抗−耐電圧特性が低下し、また、０．４５原子
％を越えると室温比抵抗が３０Ωｃｍを越えてしまうた
め好ましくない。The addition amount (z) of yttrium as a semiconducting agent is preferably 0.2 atomic% or more and 0.45 atomic% or less with respect to the Ti atomic weight of barium titanate.
If the amount of yttrium added is less than 0.2 atomic%, the specific resistance-withstand voltage characteristics deteriorate, and if it exceeds 0.45 atomic%, the room temperature specific resistance exceeds 30 Ωcm, which is not preferable.
【００２３】ＳｉＯ2 の添加量（α）は、チタン酸バリ
ウムのＴｉ原子量に対し、１．５原子％以上２．５原子
％以下が好ましい。ＳｉＯ2 量が、１．５原子％未満の
場合には比抵抗−耐電圧特性が低下し、２．５原子％を
越えると比抵抗−抵抗温度係数特性が低下する。The addition amount (α) of SiO 2 is preferably 1.5 atom% or more and 2.5 atom% or less with respect to the Ti atom weight of barium titanate. When the amount of SiO 2 is less than 1.5 atomic%, the specific resistance-withstand voltage characteristic deteriorates, and when it exceeds 2.5 atomic%, the specific resistance-resistance temperature coefficient characteristic deteriorates.
【００２４】Ｍｎの添加量（β）については、イットリ
ウム添加量に対し、１０原子％以上２０原子％以下が好
ましい。イットリウムとマンガンとは、焼結体の電気特
性に相互に影響を及ぼしあうため、マンガン量に対する
イットリウム量の比（β／ｚ）が０．１０未満の場合に
は、比抵抗−耐電圧特性あるいは比抵抗−抵抗温度係数
特性が低下し、また、比が０．２０を越えると室温比抵
抗が３０Ωｃｍを越えてしまうため、好ましくない。The addition amount (β) of Mn is preferably 10 atom% or more and 20 atom% or less with respect to the yttrium addition amount. Since yttrium and manganese mutually affect the electrical characteristics of the sintered body, when the ratio (β / z) of the amount of yttrium to the amount of manganese is less than 0.10, the specific resistance-withstand voltage characteristic or The resistivity-temperature coefficient of resistance characteristics are deteriorated, and if the ratio exceeds 0.20, the room temperature resistivity exceeds 30 Ωcm, which is not preferable.
【００２５】なお、上述した事情により、本発明方法に
おける適切な範囲は相対的数値でしか表現できないが、
一応の目安として、チタン酸バリウム系半導体磁器に含
有させる各化合物が上記記載した種類であり、通常に使
用される原料粉体を用いて固溶体粉末が得られるように
仮焼を行った場合には、仮焼によって得られる固溶体粉
末の比表面積はおおよそ１．０〜１．５ｍ2 ／ｇの範囲
となり、この際の粉砕後の適切な比表面積として、おお
よそ１．５〜３．５ｍ2 ／ｇの範囲にすれば、優れた特
性を有する磁器が得られる。Due to the above-mentioned circumstances, the appropriate range in the method of the present invention can be expressed only by relative numerical values.
As a rough guide, each compound to be contained in the barium titanate-based semiconductor porcelain is of the type described above, and when calcination is carried out so that a solid solution powder is obtained using a normally used raw material powder, The specific surface area of the solid solution powder obtained by calcination is in the range of approximately 1.0 to 1.5 m 2 / g, and the appropriate specific surface area after crushing in this case is approximately 1.5 to 3.5 m 2 / g. Within the range, a porcelain having excellent characteristics can be obtained.
【００２６】[0026]
【作用】本発明方法によれば、チタン酸バリウム系半導
体磁器において、仮焼して得られる半導体化剤含有チタ
ン酸バリウム系固溶体の原料粉体の粉砕度を制御し、粉
砕により新たに生成する反応活性なサイトの生成量を調
整することにより、電気特性の優れた磁器を得ることが
できる。さらに、上記半導体磁器の組成をも管理するこ
とにより、室温比抵抗が３０Ωｃｍ以下で、耐電圧と室
温比抵抗の比が１０以上であるとともに、抵抗温度係数
と室温比抵抗の対数値との比が１２以上である半導体磁
器を得ることができる。According to the method of the present invention, in the barium titanate-based semiconductor porcelain, the degree of pulverization of the raw material powder of the barium titanate-based solid solution containing a semiconducting agent obtained by calcination is controlled and newly generated by pulverization. By adjusting the amount of reaction-active sites produced, a porcelain having excellent electrical characteristics can be obtained. Furthermore, by controlling the composition of the above-mentioned semiconductor porcelain, the room temperature resistivity is 30 Ωcm or less, the ratio of withstand voltage to room temperature resistivity is 10 or more, and the ratio of the temperature coefficient of resistance to the logarithmic value of room temperature resistivity. It is possible to obtain a semiconductor porcelain having a value of 12 or more.
【００２７】[0027]
【実施例】以下、実施例により、本発明をさらに詳しく
述べる。 実施例 １ 〔粉砕度の調整〕出発原料として、ＢａＣＯ3 ，ＳｒＣ
Ｏ3 ，Ｐｂ3 Ｏ4 ，ＴｉＯ2 （平均粒子径０．７μ
ｍ），Ｙ（ＮＯ3 ）3 ・６Ｈ2 Ｏ，ＳｉＯ2 ，Ｍｎ（Ｎ
Ｏ3 ）2 ・６Ｈ2 Ｏを使用し、焼成後の磁器組成が、 （Ｂａ0.617 Ｓｒ0.21Ｐｂ0.17Ｙ0.003 ）ＴｉＯ3 ＋０．０２ＳｉＯ2 ＋０．０００４Ｍｎ という組成となるように各化合物を配合し、湿式ボール
ミル混合を１５時間行った。混合後、脱水乾燥し、得た
粉体を１１００℃で２時間仮焼した。仮焼粉の比表面積
は、島津製作所社製のフローソーブII ２３００を用い
て測定したところ、１．２０ｍ2 ／ｇであった。上記仮
焼粉をピンミルにより解砕した後、０．５重量％の分散
剤を添加して、純水を用いて７０重量％のスラリーに調
製した。このスラリーを原料に、表１に示す各条件にて
湿式ボールミル粉砕を行った。粉砕後のスラリーの一部
をサンプリングし、脱水乾燥した後、粉砕前の仮焼粉と
同様に比表面積を測定して粉砕度を計算した。得られた
結果を表１に示す。EXAMPLES The present invention will be described in more detail below with reference to examples. Example 1 [Adjustment of pulverization degree] As a starting material, BaCO 3 , SrC
O 3 , Pb 3 O 4 , TiO 2 (average particle size 0.7μ
m), Y (NO 3) 3 · 6H 2 O, SiO 2, Mn (N
O 3) using 2 · 6H 2 O, porcelain composition after firing was blended each compound so as to have the composition of (Ba 0.617 Sr 0.21 Pb 0.17 Y 0.003) TiO 3 + 0.02SiO 2 + 0.0004Mn, Wet ball mill mixing was carried out for 15 hours. After mixing, it was dehydrated and dried, and the obtained powder was calcined at 1100 ° C. for 2 hours. The specific surface area of the calcined powder was 1.20 m 2 / g when measured using a Flowsorb II 2300 manufactured by Shimadzu Corporation. After the calcined powder was crushed with a pin mill, 0.5% by weight of a dispersant was added, and pure water was used to prepare a 70% by weight slurry. Using this slurry as a raw material, wet ball milling was performed under the conditions shown in Table 1. A part of the pulverized slurry was sampled, dehydrated and dried, and then the specific surface area was measured in the same manner as the calcined powder before pulverization to calculate the pulverization degree. The results obtained are shown in Table 1.
【００２８】[0028]
【表１】 試料番号２、５、６、８、９、１０が、本発明方法の特徴である、粉砕度１． ２〜２．５の範囲内にある原料粉体である。[Table 1] Sample Nos. 2, 5, 6, 8, 9, and 10 are the features of the method of the present invention, the pulverization degree 1. The raw material powder is in the range of 2 to 2.5.
【００２９】〔磁器の焼成および電気特性の測定〕上記
で得られた各試料における粉砕後のスラリーに、バイン
ダーを加えて造粒し、成形圧力１０００ｋｇ／ｃｍ2 で
プレスし、直径２０ｍｍ×厚み１．０ｍｍの円板状の成
形体を得た。この成形体を３００℃／時間で昇温し、最
高保持温度で１時間保持した後、１００℃／時間で降温
し、半導体磁器を得た。最高保持温度については、１２
８０℃から１３８０℃の間で１０℃ずつ変化させたサン
プルを各々作成した。また、磁器表面を走査電子顕微鏡
により観察し、粒径範囲を求めた。[Burning of Porcelain and Measurement of Electrical Properties] A binder was added to the slurries after crushing in each of the samples obtained above to granulate, and the mixture was pressed at a molding pressure of 1000 kg / cm 2 to have a diameter of 20 mm and a thickness of 1 A disk-shaped molded body of 0.0 mm was obtained. This molded body was heated at 300 ° C./hour, held at the maximum holding temperature for 1 hour, and then cooled at 100 ° C./hour to obtain a semiconductor porcelain. 12 for maximum holding temperature
Samples were prepared by changing the temperature between 80 ° C and 1380 ° C by 10 ° C. Further, the surface of the porcelain was observed with a scanning electron microscope to determine the particle size range.
【００３０】得られた半導体磁器の両主表面にＩｎ−Ｇ
ａ合金を塗布し、室温比抵抗、耐電圧、抵抗温度係数を
測定した。耐電圧としては、試料に印加する電圧を徐々
に上昇させ、試料の破壊が生じる直前の電圧値を記載
し、抵抗温度係数〔α〕としては、Ｔ1 をキュリー温
度、Ｔ2 をキュリー温度より５０℃高い温度、Ｒ1 を温
度Ｔ1 での抵抗値、Ｒ2 を温度Ｔ2 での抵抗値として、 α ＝ ｛ｌｎ（Ｒ2 ／Ｒ1 ）／（Ｔ2 ／Ｔ1 ）｝×１００ （％／℃） で示される値を記載した。各試料において最も良好な特
性が得られた最高保持温度（最適焼成温度）の物性的特
性を表２に、その電気的特性を表３にそれぞれ示す。In-G was formed on both main surfaces of the obtained semiconductor porcelain.
Alloy a was applied, and room temperature specific resistance, withstand voltage, and resistance temperature coefficient were measured. As the withstand voltage, the voltage value immediately before the sample is destroyed by gradually increasing the voltage applied to the sample is described. As the temperature coefficient of resistance [α], T 1 is the Curie temperature and T 2 is the Curie temperature. 50 ° C. higher temperatures, the resistance value of the R 1 at a temperature T 1, as the resistance value of the R 2 at a temperature T 2, α = {ln ( R 2 / R 1) / (T 2 / T 1)} × 100 The value indicated by (% / ° C.) is described. Table 2 shows the physical properties at the maximum holding temperature (optimal firing temperature) where the best properties were obtained for each sample, and Table 3 shows the electrical properties thereof.
【００３１】[0031]
【表２】 [Table 2]
【００３２】[0032]
【表３】 [Table 3]
【００３３】表２、表３において※印を付してある、
１、３、４、７の試料番号の磁器は、粉砕度が１．２〜
２．５の範囲外である。表３から明らかなように、試料
番号２、５、６、８、９、１０の本発明の磁器は、耐電
圧と室温比抵抗との比（Ｖ／ρ）が優れている（少なく
とも１３．５以上）と共に、抵抗温度係数と室温比抵抗
の対数値との比の値（α／log ρ）も１２以上を示すと
いう、優れた特性を有している。In Tables 2 and 3, marked with *,
The porcelains of sample numbers 1, 3, 4, and 7 have a pulverization degree of 1.2 to
It is outside the range of 2.5. As is clear from Table 3, the porcelains of the present invention of Sample Nos. 2, 5, 6, 8, 9, and 10 are excellent in the ratio (V / ρ) between the withstand voltage and the room temperature specific resistance (at least 13. 5 or more), the ratio value (α / log ρ) between the temperature coefficient of resistance and the logarithm of room temperature resistivity is 12 or more, which is an excellent characteristic.
【００３４】なお、試料番号２〜７のように、ジルコニ
アが粉砕メディアである場合、蛍光Ｘ線分析法により各
試料のジルコニウム含有量を測定すると、いずれも０．
２原子％未満ではあるものの、粉砕時間に応じてコンタ
ミが生ずる。コンタミによる影響を調べるため、あらか
じめジルコニアを加えてからテフロンボールを粉砕メデ
ィアとして仮焼粉を処理したサンプルを用いて磁器を作
成し、その特性を測定したところ、得られる電気特性に
ジルコニウム含有量による影響は見られなかった。When zirconia is a crushed medium as in Sample Nos. 2 to 7, when the zirconium content of each sample is measured by a fluorescent X-ray analysis method, it is found that the zirconium content is 0.
Although it is less than 2 atomic%, contamination occurs depending on the grinding time. In order to investigate the effect of contamination, porcelain was created using a sample in which zirconia was added in advance, and then Teflon balls were used as grinding media to treat the calcined powder, and the characteristics were measured.The obtained electrical characteristics depend on the zirconium content. No impact was seen.
【００３５】〔実施例 ２〕出発原料として用いるＴｉ
Ｏ2 の平均粒子径を０．７μｍから０．３μｍのものと
した以外は、実施例１と同様の操作を行った。得られた
仮焼粉の比表面積は、１．５４ｍ2 ／ｇであった。実施
例１と同様に粉砕処理を行った後の各試料の比表面積と
粉砕度を表４に示す。Example 2 Ti used as a starting material
The same operation as in Example 1 was performed except that the average particle diameter of O 2 was changed from 0.7 μm to 0.3 μm. The specific surface area of the obtained calcined powder was 1.54 m 2 / g. Table 4 shows the specific surface area and pulverization degree of each sample after the pulverization treatment was performed in the same manner as in Example 1.
【００３６】[0036]
【表４】 [Table 4]
【００３７】試料番号１２、１３、１５、１６、１８、
１９、２０が、本発明方法の特徴である、粉砕度１．２
〜２．５の範囲内にある原料粉体である。また、各試料
において最も良好な特性が得られた磁器の物性的特性を
表５に、その電気的特性を表６に示す。Sample Nos. 12, 13, 15, 16, 18,
19 and 20 are the characteristics of the method of the present invention, and the pulverization degree is 1.2.
It is a raw material powder in the range of 2.5. In addition, Table 5 shows the physical properties of the porcelain from which the best properties were obtained in each sample, and Table 6 shows the electrical properties thereof.
【００３８】[0038]
【表５】 [Table 5]
【００３９】[0039]
【表６】 [Table 6]
【００４０】表５、表６において※印を付してある、１
１、１４、１７の試料番号の磁器は、粉砕度が１．２〜
２．５の範囲外である。表６から明らかなように、試料
番号１２、１３、１５、１６、１８、１９、２０の本発
明の磁器は、耐電圧と室温比抵抗との比（Ｖ／ρ）が優
れている（少なくとも１６以上）と共に、抵抗温度係数
と室温比抵抗の対数値との比の値（α／log ρ）も１２
以上を示すという、優れた特性を有している。1 marked with * in Tables 5 and 6
The porcelains with sample numbers 1, 14, and 17 have a pulverization degree of 1.2 to
It is outside the range of 2.5. As is clear from Table 6, the porcelains of the present invention of Sample Nos. 12, 13, 15, 16, 18, 19, and 20 are excellent in the ratio (V / ρ) between the withstand voltage and the room temperature resistivity (at least). 16 or more), and the ratio value (α / log ρ) between the temperature coefficient of resistance and the logarithm of room temperature resistivity is also 12
It has excellent characteristics of showing the above.
【００４１】また、表３や表６に示されているように、
粉砕度が本発明方法の範囲内にあり、さらに、磁器組成
が適切な場合には、出発原料の種類や大きさを調整する
ことにより、焼結体粒径をも制御でき、比抵抗−耐電圧
特性がさらに優れたものを得ることができる。Further, as shown in Table 3 and Table 6,
When the pulverization degree is within the range of the method of the present invention and the porcelain composition is appropriate, the grain size of the sintered body can be controlled by adjusting the type and size of the starting material, and the specific resistance-resistance It is possible to obtain the one having further excellent voltage characteristics.
【００４２】〔実施例 ３〕本例では、磁器組成が本発
明の範囲内でなくとも、粉砕度が本発明方法の範囲内で
あれば、従来よりも優れた電気特性を有する磁器が得ら
れることを説明する。Example 3 In this example, even if the porcelain composition is not within the range of the present invention, if the pulverization degree is within the range of the method of the present invention, a porcelain having superior electrical characteristics to the conventional one can be obtained. Explain that.
【００４３】出発原料として、ＢａＣＯ3 ，ＳｒＣ
Ｏ3 ，ＣａＣＯ3 ，Ｐｂ3 Ｏ4 ，ＴｉＯ2 （平均粒子径
０．７μｍ），Ｙ（ＮＯ3 ）3 ・６Ｈ2 Ｏ，ＳｉＯ2 ，
Ｍｎ（ＮＯ3 ）2 ・６Ｈ2 Ｏを使用し、焼成後の磁器組
成が、 （Ｂａ0.747 Ｓｒ0.08Ｐｂ0.05Ｃａ0.12Ｙ0.003 ）ＴｉＯ3 ＋０．０２ＳｉＯ2 ＋０．０００４Ｍｎ という組成となるように各化合物を配合した以外は、実
施例１と同様の操作を行った。得られた仮焼粉の比表面
積は、１．０９ｍ2 ／ｇであった。実施例１と同様に粉
砕処理を行った後の各試料の比表面積と粉砕度を表７に
示す。As a starting material, BaCO 3 , SrC
O 3 , CaCO 3 , Pb 3 O 4 , TiO 2 (average particle size 0.7 μm), Y (NO 3 ) 3 · 6H 2 O, SiO 2 ,
Mn (NO 3 ) 2 .6H 2 O was used, and the porcelain composition after firing was such that (Ba 0.747 Sr 0.08 Pb 0.05 Ca 0.12 Y 0.003 ) TiO 3 + 0.02SiO 2 + 0.0004Mn. The same operation as in Example 1 was carried out except that was added. The specific surface area of the obtained calcined powder was 1.09 m 2 / g. Table 7 shows the specific surface area and pulverization degree of each sample after the pulverization treatment was performed in the same manner as in Example 1.
【００４４】[0044]
【表７】 [Table 7]
【００４５】試料番号２２、２５、２６、２８、２９、
３０が、粉砕度１．２〜２．５の範囲内にある原料粉体
である。また、各試料において最も良好な特性が得られ
た磁器の物性的特性を表８に、その電気的特性を表９に
示す。Sample numbers 22, 25, 26, 28, 29,
30 is a raw material powder having a pulverization degree of 1.2 to 2.5. In addition, Table 8 shows the physical properties of the porcelain in which the best properties were obtained in each sample, and Table 9 shows the electrical properties thereof.
【００４６】[0046]
【表８】 [Table 8]
【００４７】[0047]
【表９】 [Table 9]
【００４８】表８、表９において※印を付してある、２
１、２３、２４、２７の試料番号の磁器は、粉砕度が
１．２〜２．５の範囲外である。表９に示したように、
粉砕度が本発明方法の範囲内にあれば、磁器組成が本発
明の範囲内でなくとも、耐電圧と室温比抵抗の比（Ｖ／
ρ）が１０以上であるような優れた電気特性を有する磁
器が得られる。2 marked with * in Tables 8 and 9
The porcelains of sample numbers 1, 23, 24, and 27 have a pulverization degree outside the range of 1.2 to 2.5. As shown in Table 9,
If the pulverization degree is within the range of the method of the present invention, even if the porcelain composition is not within the range of the present invention, the ratio of withstand voltage to room temperature specific resistance (V /
A porcelain having excellent electrical characteristics such that ρ) is 10 or more can be obtained.
【００４９】〔実施例 ４〕実施例１で用いた出発原料
と同じ原料を使用し、焼成後の磁器組成が、（Ｂａ
1-x-y-z Ｓｒx Ｐｂy Ｙz ) A ＴｉB Ｏ3 ＋αＳｉＯ2
＋βＭｎにおいて、表１０および表１１の組成となるよ
うに、各化合物を配合し、湿式ボールミル混合を１５時
間行った。これを脱水乾燥して得られた粉体を、１１０
０℃で２時間仮焼した。得られた仮焼粉をピンミルによ
り解砕後、純水と０．５重量％の分散剤を添加して７０
重量％のスラリーを調製し、これを直径１０ｍｍのジル
コニアボールを用いて、湿式ボールミルにより３時間粉
砕した。粉砕後の比表面積の測定を行い、粉砕度を計算
したところ、いずれのサンプルも１．６０〜２．００の
範囲内であった。すなわち、少なくとも粉砕度に関して
は本発明方法の特徴を有している。Example 4 Using the same starting material as used in Example 1, the porcelain composition after firing was (Ba
1-xyz Sr x Pb y Y z) A Ti B O 3 + αSiO 2
In + βMn, the compounds were blended so as to have the compositions shown in Tables 10 and 11, and wet ball mill mixing was performed for 15 hours. The powder obtained by dehydrating and drying this is 110
It was calcined at 0 ° C. for 2 hours. The calcined powder thus obtained was crushed by a pin mill, and pure water and 0.5% by weight of a dispersant were added to 70
A wt% slurry was prepared, and this was pulverized for 3 hours by a wet ball mill using zirconia balls having a diameter of 10 mm. When the specific surface area after pulverization was measured and the pulverization degree was calculated, all samples were within the range of 1.60 to 2.00. That is, at least with respect to the pulverization degree, the method of the present invention has a feature.
【００５０】[0050]
【表１０】 [Table 10]
【００５１】[0051]
【表１１】 [Table 11]
【００５２】磁器の焼成、電気特性の測定などは、実施
例１と同様の手法で行った。ただし、磁器の焼成につい
ては、最高保持温度を１３２０℃としたサンプルのみを
作成した。得られた電気特性の結果を、表１２および表
１３に示す。The firing of the porcelain and the measurement of the electrical characteristics were carried out in the same manner as in Example 1. However, regarding the firing of the porcelain, only the sample having the maximum holding temperature of 1320 ° C. was prepared. The obtained electrical property results are shown in Tables 12 and 13.
【００５３】[0053]
【表１２】 [Table 12]
【００５４】[0054]
【表１３】 [Table 13]
【００５５】表１０〜表１３において※印を付してあ
る、試料番号３１、３２、３４、３８、３９、４２、４
３、４６、４７、５３、５４、５８の磁器は、粉砕度に
ついては、本発明方法の特徴である１．２〜２．５の範
囲内であるが、磁器組成については本発明の範囲内にな
いものである。Sample numbers 31, 32, 34, 38, 39, 42, 4 marked with * in Tables 10 to 13
The porcelains of Nos. 3, 46, 47, 53, 54 and 58 have a pulverization degree within the range of 1.2 to 2.5, which is a feature of the method of the present invention, but have a porcelain composition within the scope of the present invention. It is something that is not in.
【００５６】表１２、表１３、および実施例３の結果に
示されているように、粉砕度が本発明方法の範囲内であ
り、磁器組成が適切であれば、室温比抵抗が３０Ωｃｍ
以下で、耐電圧と室温比抵抗の比が１０以上であるとと
もに、抵抗温度係数と室温比抵抗の対数値との比が１２
以上である磁器が得られ、また、たとえ磁器組成が適切
な範囲内でなくとも、さしたる特性の劣化はみられない
ことがわかる。As shown in Tables 12 and 13 and the results of Example 3, if the pulverization degree is within the range of the method of the present invention and the porcelain composition is appropriate, the room temperature resistivity is 30 Ωcm.
Below, the ratio between the withstand voltage and the room temperature specific resistance is 10 or more, and the ratio between the temperature coefficient of resistance and the logarithmic value of the room temperature specific resistance is 12 or less.
It can be seen that the above-mentioned porcelain was obtained, and that even if the porcelain composition was not within the appropriate range, no significant deterioration of the characteristics was observed.
【００５７】[0057]
【発明の効果】本発明によれば、チタン酸バリウム系半
導体磁器の製造において、仮焼して得られる半導体化剤
含有チタン酸バリウム系固溶体粉末の粉砕度を制御し、
該半導体磁器の組成を管理することにより、室温比抵抗
が３０Ωｃｍ以下で、耐電圧と室温比抵抗の比が１０以
上であるとともに、抵抗温度係数と室温比抵抗の対数値
との比が１２以上である半導体磁器組成物を得ることが
できる。According to the present invention, in the production of barium titanate-based semiconductor porcelain, the degree of pulverization of the semiconductor agent-containing barium titanate-based solid solution powder obtained by calcination is controlled,
By controlling the composition of the semiconductor porcelain, the room temperature resistivity is 30 Ωcm or less, the ratio of the withstand voltage and the room temperature resistivity is 10 or more, and the ratio of the temperature coefficient of resistance to the logarithmic value of the room temperature resistivity is 12 or more. It is possible to obtain a semiconductor porcelain composition that is
Claims (2)
に供する際の原料粉体の比表面積と、粉砕前仮焼直後の
原料粉体の比表面積との比が、焼成直前／仮焼直後の値
として、１．２以上２．５以下の範囲内に入るように、
仮焼後の原料粉体を粉砕することを特徴とするチタン酸
バリウム系半導体磁器の製造方法。1. Regarding the raw material powder used for porcelain firing, the ratio of the specific surface area of the raw material powder when it is subjected to sintering and the specific surface area of the raw material powder immediately after calcination before pulverization Immediately after that, so that it falls within the range of 1.2 or more and 2.5 or less,
A method for manufacturing a barium titanate-based semiconductor porcelain, which comprises pulverizing raw material powder after calcination.
y Ｙz ) A ＴｉB Ｏ3 ＋αＳｉＯ2 ＋βＭｎで表され、
ｘ，ｙ，ｚ，Ａ，Ｂ，α，βがそれぞれ、 ０．１２ ≦ ｘ ≦ ０．３３ ０．１２ ≦ ｙ ≦ ０．３３ ０．２５ ≦ ｘ＋ｙ ≦ ０．４５ ０．００２ ≦ ｚ ≦ ０．００４５ ０．９９５ ≦ Ａ／Ｂ ≦ １．００５ ０．０１５ ≦ α ≦ ０．０２５ ０．１０ ≦ β／ｚ ≦ ０．２０ の範囲内である、請求項１記載のチタン酸バリウム系半
導体磁器の製造方法。2. The porcelain composition is (Ba 1-xyz Sr x Pb
y Y z ) A Ti B O 3 + αSiO 2 + βMn,
x, y, z, A, B, α, β are respectively 0.12 ≤ x ≤ 0.33 0.12 ≤ y ≤ 0.33 0.25 ≤ x + y ≤ 0.45 0.002 ≤ z ≤ 0 2. The barium titanate-based semiconductor porcelain according to claim 1, which is within a range of .0045 0.995 ≤ A / B ≤ 1.005 0.015 ≤ α ≤ 0.025 0.10 ≤ β / z ≤ 0.20. Manufacturing method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7029930A JPH08255703A (en) | 1995-01-25 | 1995-01-25 | Method for manufacturing barium titanate-based semiconductor porcelain |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7029930A JPH08255703A (en) | 1995-01-25 | 1995-01-25 | Method for manufacturing barium titanate-based semiconductor porcelain |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08255703A true JPH08255703A (en) | 1996-10-01 |
Family
ID=12289715
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7029930A Pending JPH08255703A (en) | 1995-01-25 | 1995-01-25 | Method for manufacturing barium titanate-based semiconductor porcelain |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08255703A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013535398A (en) * | 2010-07-30 | 2013-09-12 | エルジー イノテック カンパニー リミテッド | Method for producing sintered silicon carbide using balls |
-
1995
- 1995-01-25 JP JP7029930A patent/JPH08255703A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013535398A (en) * | 2010-07-30 | 2013-09-12 | エルジー イノテック カンパニー リミテッド | Method for producing sintered silicon carbide using balls |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101389581A (en) | Semiconducting Ceramic Components | |
| KR101361358B1 (en) | Semiconductor ceramic composition and method for producing the same | |
| US6221800B1 (en) | Method of producing PTC semiconducting ceramic | |
| WO2010067866A1 (en) | Semiconductor ceramic and positive temperature coefficient thermistor | |
| Duran et al. | Large electromechanical anisotropic modified lead titanate ceramics: Part 1 Processing | |
| CN116534893A (en) | Solid phase synthesis method of calcium doped barium titanate powder | |
| JPH0354165A (en) | PTC porcelain composition and its manufacturing method | |
| JPH08255703A (en) | Method for manufacturing barium titanate-based semiconductor porcelain | |
| JP3974952B2 (en) | Method for manufacturing piezoelectric body | |
| JPS597665B2 (en) | High dielectric constant porcelain composition | |
| JPH07277822A (en) | Piezoelectric element material and manufacturing method thereof | |
| JP2000086336A (en) | Manufacturing method of PTC thermistor | |
| JP2679449B2 (en) | Semiconductor porcelain having positive temperature coefficient of resistance and manufacturing method thereof | |
| JP2976702B2 (en) | Semiconductor porcelain composition | |
| JPH09278535A (en) | Manufacturing method of ceramics | |
| JP2004299916A (en) | Method for producing oxide powder having perovskite structure | |
| JPH07297009A (en) | Positive temperature coefficient thermistor and manufacturing method thereof | |
| JP2000264726A (en) | Semiconductor porcelain | |
| CN118955130B (en) | Gadolinium-doped high-energy-storage relaxation antiferroelectric sodium niobate-based ceramic material and preparation method and application thereof | |
| JPH07335404A (en) | Manufacturing method of positive temperature coefficient thermistor | |
| JPH05213666A (en) | Dielectric porcelain composition and its production | |
| Keizer et al. | On the defect model and the dielectric properties of lanthana substituted lead titanate ceramics | |
| JP2682824B2 (en) | Method for manufacturing grain boundary layer insulated semiconductor ceramic capacitor | |
| Moreira et al. | Dielectric properties of (Pb, Ba)(Zr, Ti) O/sub 3/ceramics | |
| JPH1072254A (en) | Method for producing barium titanate-based semiconductor porcelain |