JPS6191016A - Production of dielectric material fine powder - Google Patents

Production of dielectric material fine powder

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Publication number
JPS6191016A
JPS6191016A JP21364984A JP21364984A JPS6191016A JP S6191016 A JPS6191016 A JP S6191016A JP 21364984 A JP21364984 A JP 21364984A JP 21364984 A JP21364984 A JP 21364984A JP S6191016 A JPS6191016 A JP S6191016A
Authority
JP
Japan
Prior art keywords
solution
water
fine particles
aqueous solution
chloride
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
Application number
JP21364984A
Other languages
Japanese (ja)
Other versions
JPH06649B2 (en
Inventor
Akira Kamihira
上平 暁
Hiroshi Yamanoi
山ノ井 博
Masayuki Suzuki
真之 鈴木
Hidemasa Tamura
英雅 田村
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Sony Corp
Original Assignee
Sony Corp
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Publication date
Application filed by Sony Corp filed Critical Sony Corp
Priority to JP21364984A priority Critical patent/JPH06649B2/en
Publication of JPS6191016A publication Critical patent/JPS6191016A/en
Publication of JPH06649B2 publication Critical patent/JPH06649B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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  • Inorganic Insulating Materials (AREA)

Abstract

PURPOSE:To produce dielectric material fine powder having a small amount of Cl, by hydrolyzing Ti or Zr chloride in an aqueous solution, alkalizing it to remove Cl and reacting the solution with a specific water-soluble salt. CONSTITUTION:An aqueous solution of Ti or Zr chloride (e.g., TiCl4, or ZrCl4) is hydrolyzed with NH4OH, adjusted with an alkalizing agent (e.g., NaOH) to >=7.1pH, washed with water, and decanted, to remove Cl ion. The solution is reacted with at least one water-soluble salt [e.g., Ba(OH)2] of Ba, Sr, and Ca in an amount approximately equimolar with Ti or Zr in a strongly alkali aqueous solution. Consequently, a molded article of ceramic condenser having high reliability free from deterioration resulting form Cl is prepared.

Description

【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、チタン酸バリウム微粒子、チタン酸ストロン
チウム微粒子、ジルコニウム酸ノクリウム微粒子等の誘
電体微粒子の製造方法に関する。
DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing dielectric fine particles such as barium titanate fine particles, strontium titanate fine particles, and nocurium zirconate fine particles.

〔従来の技術〕[Conventional technology]

本出願人は、特願昭57−147226 (チタン酸)
4リウム微粒子の製造方法)、特願昭57−15124
0(チタン酸カルシウム微粒子の製造方法)、特願昭5
7−156315 (チタン酸ストロンチウム微粒子の
製造方法)、特願昭57−219540 (ジルコニウ
ム酸バリウム微粒子の製造方法)等において、湿式合成
法による誘電体微粒子の製造方法を提案した。
The applicant has filed a patent application No. 57-147226 (titanic acid).
(Method for producing 4-lium fine particles), patent application No. 57-15124
0 (Production method of calcium titanate fine particles), patent application 1973
No. 7-156315 (method for manufacturing strontium titanate fine particles), Japanese Patent Application No. 57-219540 (manufacturing method for barium zirconate fine particles), etc., proposed a method for manufacturing dielectric fine particles by a wet synthesis method.

これらの誘電体微粒子の製造方法において、Ti(又は
Zr)の原料として塩化物を使用した場合の製造方法は
、大路次の通シである。
In the manufacturing method of these dielectric fine particles, when chloride is used as a raw material for Ti (or Zr), the manufacturing method is as follows by Ohji.

先ず、Ti(J4 (又は、ZrCl14 、 Zr0
CJ!2 ・8H20等)を加水分解した後、NaOH
、KOH等のアルカリ剤を使用して中和する。次に、T
 i CJ14と等モル黄のBa (又はCa 、 S
r等)を加えた後、NaOH、KOH等のアルカリ剤で
−を強アルカリ性側にして、加熱9反応させる。この後
、デカンテーションによる水洗、濾過、乾燥を行って、
例えばチタン酸バリウムBaTiO3微粒子を得る。
First, Ti(J4 (or ZrCl14, Zr0
CJ! 2 ・8H20 etc.), then NaOH
, neutralize using an alkaline agent such as KOH. Next, T
i CJ14 and equimolar yellow Ba (or Ca, S
After adding (r, etc.), use an alkaline agent such as NaOH or KOH to make - to the strongly alkaline side, and heat for 9 reactions. After that, wash with water by decantation, filter, and dry.
For example, barium titanate BaTiO3 fine particles are obtained.

〔発明が解決しようとする問題点〕[Problem that the invention seeks to solve]

上述したように、Ti(又はZr )の原料として塩化
物を使用して製造した誘電体微粒子を螢光X線分析装置
で測定すると、微量のClが検出される。
As described above, when dielectric fine particles manufactured using chloride as a Ti (or Zr) raw material are measured with a fluorescent X-ray analyzer, a trace amount of Cl is detected.

このC1は、原料のチタン塩化物(又はジルコニウム塩
化物)に由来するものであると考えられる。
This C1 is thought to be derived from titanium chloride (or zirconium chloride) as a raw material.

C11o存在は、コンデンサ、セラミック成形品等に加
工した後、経時変化による信頼性劣化の原因ともなり得
るので、CP量はできるだけ少ないことが望ましい。ま
た、ファインセラミックス製品の原料として使用する場
合においても、この(Jの存在が問題となシ得る場合が
ある。
Since the presence of C11o can cause reliability deterioration due to changes over time after being processed into capacitors, ceramic molded products, etc., it is desirable that the amount of CP be as small as possible. Furthermore, even when used as a raw material for fine ceramic products, the presence of (J) may pose a problem.

本発明は、上記問題点を解決することができる誘電体微
粒子の製造方法を提供するものである。
The present invention provides a method for producing dielectric fine particles that can solve the above problems.

〔問題点を解決するための手段〕[Means for solving problems]

本発明においては、チタン又はジルコニウムの塩化物(
例、tば、TiCff14 、 ZrCl4 、 Zr
0CI!2118 H2O等)を水溶液中で加水分解し
た後、この水溶液を7に−j)り剤(NaOH、KOH
等)でpH7,1以上のアルカリ性とし、この状態で水
洗、デカンテーションを行って塩素イオンを除去する。
In the present invention, titanium or zirconium chloride (
Examples, tba, TiCff14, ZrCl4, Zr
0CI! 2118 H2O, etc.) in an aqueous solution, and then add this aqueous solution to 7-j)
etc.) to make it alkaline to pH 7.1 or higher, and in this state, wash with water and decantation to remove chlorine ions.

引き続き、バリウム、ストロンチウム、カルシウムの水
溶性塩のうちの少くとも1つを加え、強アルカリ性水溶
液中で反応させて所望の誘電体微粒子を得る。
Subsequently, at least one of water-soluble salts of barium, strontium, and calcium is added and reacted in a strongly alkaline aqueous solution to obtain desired dielectric fine particles.

得られる誘電体微粒子をABO3とした場合(A:Ba
 、 Sr 、 Ca、  B: Ti 、 Zr)、
単−系ノミナらず、複合系の微粒子の製造にも適用する
ことができる。
When the obtained dielectric fine particles are ABO3 (A: Ba
, Sr, Ca, B: Ti, Zr),
It can be applied to the production of not only single nanoparticles but also composite microparticles.

なお、バリウムの水溶性塩としては、例えば、Ba(N
O3)2 、 Ba(OH)2 、 BaCj!2 、
 Ba(CH3COO)2を使用することができる。ま
た、ストロンチウムの水溶性塩としては、例えばSr(
NO3)2 、 Sr(OH)2゜5rCj!2 、5
r(CH3COO)2 、 SrOを使用することがで
きる。カルシウムの水溶性塩としては、例えばCa(N
O3)2 、 Ca(OH)2 、 CaCj!2 、
 Ca(CH3COO)2 。
In addition, as a water-soluble salt of barium, for example, Ba(N
O3)2, Ba(OH)2, BaCj! 2,
Ba(CH3COO)2 can be used. In addition, as a water-soluble salt of strontium, for example, Sr(
NO3)2, Sr(OH)2゜5rCj! 2, 5
r(CH3COO)2, SrO can be used. Examples of water-soluble salts of calcium include Ca(N
O3)2, Ca(OH)2, CaCj! 2,
Ca(CH3COO)2.

CaOを使用することができる。CaO can be used.

〔作用〕[Effect]

チタン又はジルコニウムの原料として塩化物を使用する
誘電体微粒子の製造方法において、従来塩化物を加水分
解し、アルカリで中和するとCPがTi0Cj!2など
の形で残存し、合成反応時にCQが結晶中に取り込まれ
たり、結晶表面に吸着されて、反応後の水洗でも除去さ
れないため、得られた誘電体微粒子中にCPが残留する
という問題点が生じていた。しかるに、本発明において
は、塩化物を加水分解した後の溶液を中性ではなく、ア
ルカリ性側にするため、Cj!が残存し難くなり、水洗
、デカンテーションを行うことによシ溶液中のCIAを
大幅に除去することができる。従って、得られる誘電体
微粒子中のCRの残留量も低(抑えることが可能になる
In a method for producing dielectric fine particles using chloride as a raw material for titanium or zirconium, conventionally, when the chloride is hydrolyzed and neutralized with an alkali, CP is Ti0Cj! 2, etc., and CQ is incorporated into the crystal during the synthesis reaction or adsorbed to the crystal surface and is not removed even after washing with water after the reaction, resulting in the problem that CP remains in the obtained dielectric fine particles. A dot had appeared. However, in the present invention, in order to make the solution after hydrolyzing chloride not neutral but alkaline, Cj! It becomes difficult for CIA to remain in the solution, and CIA in the solution can be largely removed by washing with water and decantation. Therefore, the amount of CR remaining in the obtained dielectric fine particles can also be kept low.

〔実施例〕〔Example〕

実施例1 50y−のTiCβ4を10ofの水に溶かした溶液に
NH,OHを加えて加水分解させ、−を9.5とした。
Example 1 NH and OH were added to a solution of 50y- TiCβ4 dissolved in 10of water to cause hydrolysis, and - was adjusted to 9.5.

そして、この沈殿が生成した溶液に水洗とデカンテーシ
ョンを繰シ返し、−を7とした。次に、溶液中のTiと
略等−T−/I/量(0,95) OBa (OH)2
を加え、KOH溶液でpi(14とした。この溶液を9
0Cで3時間反応させ、生成した沈殿に濾過、水洗を行
った後、100Cで1日乾燥させた。
Then, the solution in which this precipitate was generated was repeatedly washed with water and decanted, and the value of - was set to 7. Next, approximately equal to Ti in the solution -T-/I/amount (0,95) OBa (OH)2
was added and adjusted to pi (14) with KOH solution.This solution was adjusted to 9
After reacting at 0C for 3 hours, the resulting precipitate was filtered, washed with water, and then dried at 100C for 1 day.

得られた微粒子をX線回折によシ分析した結果によると
、この微粒子はBaTiO3であることが確認できた。
According to the results of X-ray diffraction analysis of the obtained fine particles, it was confirmed that the fine particles were BaTiO3.

また、粒子サイズは、200〜300 Xであった。Moreover, the particle size was 200-300×.

実施例2 50y−のT+(J!4を200?の水に溶かした溶液
にNa OH溶液を加えて加水分解させ、−を9.5と
した。
Example 2 A NaOH solution was added to a solution of 50y- T+ (J!4 dissolved in 200? water to cause hydrolysis, and - was adjusted to 9.5.

そして、この沈殿が生成した溶液に水洗とデカンテーシ
ョンを繰シ返し、−を7とした。次に、BaOを加え、
NaOH溶液でpH13,7とした後、95Cで2時間
反応させた。生成した沈殿に濾過、水洗を行い、100
Cで1日乾燥させた。
Then, the solution in which this precipitate was generated was repeatedly washed with water and decanted, and the value of - was set to 7. Next, add BaO,
After adjusting the pH to 13.7 with a NaOH solution, the mixture was reacted at 95C for 2 hours. The generated precipitate was filtered and washed with water, and
It was dried at C for 1 day.

得られた微粒子をX線回折によシ分析した結果によると
、この微粒子はBaT i03であることが確認できた
二また、粒子サイズは、200〜300Xであった。
According to the results of X-ray diffraction analysis of the obtained fine particles, it was confirmed that the fine particles were BaTi03, and the particle size was 200 to 300X.

次に、表1に上記実施例1及び2で得られたBaTiO
3微粒子について、螢光X線分析によシ残留塩素量を測
定した結果を比較例(加水分解直後の溶液の−は7)と
併せて示す。この表から、加水分解後の溶液をアルカリ
性にし、水洗とデカンテーションを施すことが、得られ
たBaTiO3微粒子中の残留塩素量を減少させるのに
有効であることが表1 実施例3 50テのTiCJ!4を100?の水に溶かした溶液に
NH4OHを加えて加水分解させ、−を9.5とした。
Next, Table 1 shows the BaTiO obtained in Examples 1 and 2 above.
The results of measuring the amount of residual chlorine for the 3 fine particles by fluorescent X-ray analysis are shown together with a comparative example (- of the solution immediately after hydrolysis is 7). From this table, it can be seen that making the solution after hydrolysis alkaline, washing with water and decantation is effective in reducing the amount of residual chlorine in the obtained BaTiO3 fine particles. TiCJ! 4 to 100? NH4OH was added to a solution dissolved in water to cause hydrolysis, and - was adjusted to 9.5.

そして、この沈殿が生成した溶液に水洗とデカンテーシ
ョンを繰り返して−を7とした。次に、この溶液o’r
iに対して、Sr/Ti = 1.05 (モル比)と
なるSr(OH)2を加え、KOH溶液でPI(を14
とした。
Then, water washing and decantation were repeated to the solution in which this precipitate was generated, and - was set to 7. Next, this solution o'r
Sr(OH)2 was added to Sr/Ti = 1.05 (molar ratio) to i, and PI (14
And so.

この溶液を95Cで4時間反応させた後、生成した沈殿
に濾過、水洗を行い、100Cで1日乾燥させた。
After reacting this solution at 95C for 4 hours, the resulting precipitate was filtered, washed with water, and dried at 100C for 1 day.

得られた微粒子をX線回折によシ分析した結果によると
、この微粒子は5rTi03であることが確認できた。
According to the results of X-ray diffraction analysis of the obtained fine particles, it was confirmed that the fine particles were 5rTi03.

また、粒子サイズは、100〜200Xであつた。Moreover, the particle size was 100-200X.

実施例4 50テのT i CR4を2001の水に溶かした溶液
にNaOH溶液を加えて加水分解させ、−を9,5とし
た。
Example 4 A NaOH solution was added to a solution of 50% T i CR4 dissolved in 2001% water for hydrolysis, and - was adjusted to 9.5.

そして、この沈殿が生じた溶液に水洗とデカンテーショ
ンを繰シ返して−を7とした。次に、この溶液中のTi
と等モル量の5rCR2を加え、NaOH溶液でpi−
114とした。100Cで3時間反応きせた後、生成し
た沈殿に濾過、水洗を行い、100Cで1日乾燥させた
Then, the solution in which the precipitate had formed was repeatedly washed with water and decanted to give a value of -7. Next, Ti in this solution
Add an equimolar amount of 5rCR2 to pi-
It was set at 114. After reacting at 100C for 3 hours, the resulting precipitate was filtered, washed with water, and dried at 100C for 1 day.

X線回折による分析結果によると、この微粒子は5rT
i03であることが確認できた。
According to the analysis results by X-ray diffraction, this fine particle has a 5rT
I was able to confirm that it was i03.

次に、表2に上記実施例3及び4で得られた5rTi0
3微粒子について、螢光X線分析によシ残留塩素量を測
定した結果を比較例(加水分解直後の−は7)と併せて
示す。
Next, Table 2 shows the 5rTi0 obtained in Examples 3 and 4 above.
The results of measuring the amount of residual chlorine using fluorescent X-ray analysis for the 3 fine particles are shown together with a comparative example (- is 7 immediately after hydrolysis).

表2 実施例5 50?のTiCff14を100y−の水に溶かした溶
液にNH4OHを加えて加水分解させ、−を9.5とし
た。
Table 2 Example 5 50? NH4OH was added to a solution of TiCff14 dissolved in 100y- of water to hydrolyze it, and - was adjusted to 9.5.

そして、この沈殿が生じた溶液に水洗とデカンテーショ
ンを繰シ返して−を7とした。次に、この溶液中のTi
に対してモル比で1.05となるCa(OH)2を加え
、NaOH溶液でpH14とした。この溶液を95Cで
4時間反応させた後、生成した沈殿に濾過、水洗を行い
、100Cで1日乾燥させた。
Then, the solution in which the precipitate had formed was repeatedly washed with water and decanted to give a value of -7. Next, Ti in this solution
Ca(OH)2 was added thereto at a molar ratio of 1.05, and the pH was adjusted to 14 with NaOH solution. After reacting this solution at 95C for 4 hours, the resulting precipitate was filtered, washed with water, and dried at 100C for 1 day.

得られた微粒子をX線回折によシ分析した結果によると
、この微粒子はCaTiO3であることが確認できた。
According to the results of X-ray diffraction analysis of the obtained fine particles, it was confirmed that the fine particles were CaTiO3.

また、この微粒子のサイズは、1〜3μmであった。Moreover, the size of this fine particle was 1 to 3 μm.

実施例6 50fPのTiC&!4を2001の水に溶かした溶液
にNaOH溶液を加えて加水分解させ、−を9.5とし
た。
Example 6 50 fP TiC&! A NaOH solution was added to a solution of 4 dissolved in 2001 in water to cause hydrolysis, and - was adjusted to 9.5.

そして、この沈殿が生じた溶液に水洗とデカンテーショ
ンを繰シ返して−を7とした。次に、この溶液中のTi
と等モル量のCaCff12を加え、NaOH溶液でp
l−114とした。この溶液を100Cで3時間反応さ
せた後、生成した沈殿に濾過、水洗を行い、100Cで
1日乾燥させた。
Then, the solution in which the precipitate had formed was repeatedly washed with water and decanted to give a value of -7. Next, Ti in this solution
Add equimolar amount of CaCff12 to p
It was designated as l-114. After reacting this solution at 100C for 3 hours, the resulting precipitate was filtered, washed with water, and dried at 100C for 1 day.

X線回折による分析結果によると、この微粒子はCaT
iO3であることが確認できた。
According to the analysis results by X-ray diffraction, this fine particle is CaT.
It was confirmed that it was iO3.

次に、表3に上記実施例5及び6で得られたCaTiO
3微粒子について、螢光X線分析によシ残留塩素量を測
定した結果を比較例(加水分解直後の−は7)と併せて
示す。
Next, Table 3 shows the CaTiO obtained in Examples 5 and 6 above.
The results of measuring the amount of residual chlorine using fluorescent X-ray analysis for the 3 fine particles are shown together with a comparative example (- is 7 immediately after hydrolysis).

実施例7 55.74PのZrCj!4を水に溶解した50ONの
溶液から40m1を採取し、この中にLiOH溶液を加
えて加水分解させ、−を9.5とした。そして、この沈
殿が生じた溶液に水洗とデカンテーションを繰シ返して
−を7とした。この白色懸濁液にBa (OH) 2・
8H20を9.054 P (Ba/ Zr = 1.
5 )を加えLiOH溶液でpJ(14とした。この溶
液を98Cで8時間反応させた後、生成した沈殿にデカ
ンテーション、濾過を行い、乾燥させた。
Example 7 ZrCj of 55.74P! 40 ml was collected from a 50ON solution of 4 dissolved in water, and a LiOH solution was added thereto to hydrolyze it, and - was adjusted to 9.5. Then, the solution in which the precipitate had formed was repeatedly washed with water and decanted to give a value of -7. This white suspension contains Ba (OH) 2.
8H20 to 9.054 P (Ba/Zr = 1.
5) and adjusted to pJ (14) with LiOH solution. After reacting this solution at 98C for 8 hours, the resulting precipitate was decanted, filtered, and dried.

得られた微粒子をX線回折により分析した結果によると
、この微粒子はBaZr0aであることが確認できた。
According to the results of analyzing the obtained fine particles by X-ray diffraction, it was confirmed that the fine particles were BaZr0a.

また、粒子サイズは、2〜3Rであった。Moreover, the particle size was 2-3R.

螢光X線分析により残留塩素量を測定した結果によると
、本製造方法によI)得られたBaZrO3微粒子中の
残留塩素量は、大幅に減少していることが確認できた。
According to the results of measuring the amount of residual chlorine by fluorescent X-ray analysis, it was confirmed that the amount of residual chlorine in the BaZrO3 fine particles obtained by the present production method (I) was significantly reduced.

〔発明の効果〕〔Effect of the invention〕

本発明によれば、訪電体微粒子中の塩素残留量が大幅に
減少するため、塩素に原因する特性の劣化は生ぜず、信
頼性の高いコンデンサ、セラミック成形品等を提供する
ことができる。また、CPを除去する工程を付加するの
みでよく、本出願人が提案した湿式合成法をそのまま採
用することができる。
According to the present invention, since the residual amount of chlorine in the fine particles of the current-visiting body is significantly reduced, deterioration of characteristics caused by chlorine does not occur, and highly reliable capacitors, ceramic molded products, etc. can be provided. Further, it is only necessary to add a step of removing CP, and the wet synthesis method proposed by the present applicant can be adopted as is.

Claims (1)

【特許請求の範囲】[Claims]  チタン又はジルコニウムの塩化物を水溶液中で加水分
解した後、該水溶液を一旦アルカリ性にして塩素イオン
を除去し、引き続きバリウム、ストロンチウム、カルシ
ウムの水溶性塩のうちの少くとも1つを加え、強アルカ
リ性水溶液中で反応させることを特徴とする誘電体微粒
子の製造方法。
After hydrolyzing titanium or zirconium chloride in an aqueous solution, the aqueous solution is once made alkaline to remove chlorine ions, and then at least one of water-soluble salts of barium, strontium, and calcium is added to make it strongly alkaline. A method for producing dielectric fine particles characterized by reaction in an aqueous solution.
JP21364984A 1984-10-12 1984-10-12 Method for producing fine dielectric particles Expired - Fee Related JPH06649B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP21364984A JPH06649B2 (en) 1984-10-12 1984-10-12 Method for producing fine dielectric particles

Applications Claiming Priority (1)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6374915A (en) * 1986-07-14 1988-04-05 キヤボツト コ−ポレ−シヨン Manufacture of diatomic cation titanate
FR2659641A1 (en) * 1990-03-14 1991-09-20 Rhone Poulenc Chimie PROCESS FOR PREPARING A DIVALENT OR TRIVALENT CATION TITANATE.
JPH0489317A (en) * 1990-07-30 1992-03-23 Denki Kagaku Kogyo Kk Easily-sintering powder material for microwave dielectric material
EP1013609A1 (en) * 1998-05-20 2000-06-28 Toho Titanium Co., Ltd. Method for producing barium titanate powder
WO2015122180A1 (en) * 2014-02-14 2015-08-20 富士フイルム株式会社 Manufacturing method for strontium titanate fine particles

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6374915A (en) * 1986-07-14 1988-04-05 キヤボツト コ−ポレ−シヨン Manufacture of diatomic cation titanate
FR2659641A1 (en) * 1990-03-14 1991-09-20 Rhone Poulenc Chimie PROCESS FOR PREPARING A DIVALENT OR TRIVALENT CATION TITANATE.
JPH0489317A (en) * 1990-07-30 1992-03-23 Denki Kagaku Kogyo Kk Easily-sintering powder material for microwave dielectric material
EP1013609A1 (en) * 1998-05-20 2000-06-28 Toho Titanium Co., Ltd. Method for producing barium titanate powder
EP1013609A4 (en) * 1998-05-20 2007-12-19 Toho Titanium Co Ltd Method for producing barium titanate powder
WO2015122180A1 (en) * 2014-02-14 2015-08-20 富士フイルム株式会社 Manufacturing method for strontium titanate fine particles
JP2015151303A (en) * 2014-02-14 2015-08-24 富士フイルム株式会社 Method for producing strontium titanate fine particles

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