JP3412186B2 - Preparation of composite perovskite oxide powder - Google Patents
Preparation of composite perovskite oxide powderInfo
- Publication number
- JP3412186B2 JP3412186B2 JP13592893A JP13592893A JP3412186B2 JP 3412186 B2 JP3412186 B2 JP 3412186B2 JP 13592893 A JP13592893 A JP 13592893A JP 13592893 A JP13592893 A JP 13592893A JP 3412186 B2 JP3412186 B2 JP 3412186B2
- Authority
- JP
- Japan
- Prior art keywords
- compound
- powder
- precursor solution
- oxide powder
- composite perovskite
- 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.)
- Expired - Lifetime
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- Compositions Of Oxide Ceramics (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Description
【0001】[0001]
【産業上の利用分野】本発明は、複合ペロブスカイト型
酸化物微粉体の製造方法に関する。さらに詳しくは、表
面活性が高く易焼結で微細な複合ペロブスカイト型酸化
物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 producing composite perovskite type oxide fine powder. More specifically, the present invention relates to a method for producing a complex perovskite type oxide which has high surface activity and is easily sintered and fine.
【0002】[0002]
【従来の技術】最近の電子機器の小型化に伴い電子部品
に於ても小型化の要望が強く、積層セラミック部品でも
年々小型化のものへのニーズが増加している。こうした
ニーズに答える為に、微細で、低温で焼結させることが
可能で且つ均質な粉体が要求されて来る。従来の方法で
製造された粉体では粒径が粗い、均質性に欠ける或いは
焼成温度が高い等の問題点を抱えていて充分に満足出来
るものでない。鉛含有複合ペロブスカイト型酸化物粉体
の製造方法については非常に多くの提案があり、下記の
ごとく大別される。
酸化物固相法
構成成分元素の酸化物、炭酸塩等を固相で混合仮焼して
原料粉体とする方法。
共沈法
成分元素の水可溶性化合物を含有する混合水溶液のpH
を調整して、それぞれの水酸化物を共沈させ、該共沈酸
化物を仮焼して原料粉体を得る方法。
有機金属法
成分元素のアルコキシド、有機溶剤可溶性化合物を含有
する有機溶剤を熱分解して生成するもしくは加水分解し
て生成する沈澱粉体を仮焼して原料粉体を得る方法。2. Description of the Related Art With the recent miniaturization of electronic equipment, there is a strong demand for miniaturization of electronic components, and the demand for miniaturized monolithic ceramic components is increasing year by year. In order to meet these needs, fine powders that can be sintered at low temperature and that are homogeneous are required. The powder produced by the conventional method has problems such as coarse particle size, lack of homogeneity, and high firing temperature, and is not fully satisfactory. There are numerous proposals for the method for producing the lead-containing composite perovskite type oxide powder, which are roughly classified as follows. Oxide solid phase method A method in which the oxides, carbonates, etc. of the constituent elements are mixed and calcined in the solid phase to obtain raw material powder. Coprecipitation method pH of mixed aqueous solution containing water-soluble compound of element
Is adjusted to coprecipitate each hydroxide, and the coprecipitated oxide is calcined to obtain a raw material powder. Organic metal method A method for obtaining a raw material powder by calcination of a precipitated powder produced by thermal decomposition or hydrolysis of an organic solvent containing an alkoxide of a component element and an organic solvent-soluble compound.
【0003】[0003]
【発明が解決しようとする課題】酸化物固相法は、種々
の組成の原料粉体を安価に製造し得る方法であり、工業
的に広く用いられている方法であるが、得られる粉体は
粒径が大きく粒度分布が広く粒子形状がバラバラである
為磁器製造時の成形性及び焼結性が悪く、高い密度の磁
器が得られ難い。この方法は副生成物としてパイロクロ
ア相が生成し、複合ペロブスカイト単一相とはならず、
この副生成物相をなくする為高温で仮焼する必要があ
る。その為生成した粉体は表面活性が低い粉体となって
しまうので、高温で焼成しないと焼結しない。高温で焼
成する為、焼成中に鉛の蒸発による組成ズレが生ずる等
の不都合な点が多々ある。しかも原料粉体を分子レベル
で均一に分散させることはとても不可能である。また生
成する原料粉体は粗大である為、使用可能な状態にする
のに機械的な粉砕が必要となって来る。この粉砕工程か
らくる不純物混入という問題点も抱えている。The oxide solid phase method is a method that can inexpensively produce raw material powders having various compositions, and is a method that is widely used industrially. Has a large particle size, a wide particle size distribution, and different particle shapes, so that the formability and sinterability during porcelain production are poor, and it is difficult to obtain a high density porcelain. In this method, a pyrochlore phase is produced as a by-product, and a composite perovskite single phase is not formed,
It is necessary to calcine at high temperature to eliminate this by-product phase. Therefore, the generated powder becomes a powder having low surface activity, so that it does not sinter unless it is fired at a high temperature. Since firing is carried out at a high temperature, there are many inconveniences such as composition deviation due to evaporation of lead during firing. Moreover, it is very impossible to uniformly disperse the raw material powder at the molecular level. Further, since the raw material powder produced is coarse, mechanical pulverization becomes necessary to make it usable. There is also a problem of mixing impurities from this crushing process.
【0004】共沈法は粒子形状及び粒径の揃った原料粉
体を比較的容易に得られる方法であって、工業的にも用
いられている。しかしながら、該方法に於ては金属元素
の種類によってその水酸化物の溶解度積を異にする為、
化学量論的に組成のコントロールされた共沈水酸化物を
種々の組成について生成させることが困難である。構成
元素の水酸化物として沈澱するpH領域が異なる為、構
成元素の水酸化物が生成pHの低い順に生成していくの
で全ての元素が同時に生成しない。よって、この方法は
酸化物固相法に比べると分散性は向上しているものの共
沈というよりも各元素の水酸化物の沈澱がかなり均一に
分散した状態で混合している状態である。よって、この
方法でも分子(原子)レベルでの均一分散を行うことは不
可能である。また、この方法で得られた洗浄脱水後の乾
燥ケーキは緻密に凝集した塊である。従って、仮焼工程
で簡単に破砕されない焼結に近い状態の凝集体になって
いる。それ故に簡単な粉砕処理をしただけでは微細な酸
化物粉体を得ることは困難である。酸化物固相法と同じ
くエネルギーの大きな粉砕装置を用いねばならず不純物
の混入という問題を避けることが出来ない。よって、こ
の方法も良い方法とは言い難い。The coprecipitation method is a method for relatively easily obtaining a raw material powder having a uniform particle shape and particle size, and is also used industrially. However, in this method, the solubility product of the hydroxide varies depending on the type of metal element,
It is difficult to produce stoichiometrically controlled coprecipitated hydroxides for various compositions. Since the pH regions which are precipitated as hydroxides of the constituent elements are different, the hydroxides of the constituent elements are generated in the ascending order of pH, so that not all elements are generated at the same time. Therefore, in this method, the dispersibility is improved as compared with the oxide solid-phase method, but rather than coprecipitation, the hydroxide precipitates of the respective elements are mixed in a fairly uniformly dispersed state. Therefore, even with this method, it is impossible to perform uniform dispersion at the molecular (atomic) level. The dried cake obtained by this method after washing and dehydration is a densely aggregated mass. Therefore, the agglomerates are in a state close to sintering that is not easily crushed in the calcination step. Therefore, it is difficult to obtain a fine oxide powder only by performing a simple pulverization process. As with the oxide solid-phase method, a crushing device with large energy must be used, and the problem of mixing impurities cannot be avoided. Therefore, this method is not good.
【0005】有機金属法は、生成する酸化物粉体の粒径
が小さく、粒子形状の揃った化学量論的に組成のコント
ロールされた高い焼結性の粉体が得られる方法であり、
標準組成の粉体を合成する為に実験室等に於て広く採用
されている方法である。しかしながら、原料のアルコキ
シドが極めて高価であったり、金属種によっては有機溶
剤可溶なアルコキシドの合成が不可能であったり、或い
は鉛アルコキシドの様に有害性が非常に強い等の点が多
々あり、工業的な方法ではない。またアルコキシドは湿
気に対して非常に敏感であるので、取扱いが非常に難し
い。反応を行うにも大気中の湿気を考慮した装置を考え
ねばならず装置自体が高価なものになってしまう。The organometallic method is a method for obtaining a highly sinterable powder having a small particle size of the oxide powder to be produced and a uniform stoichiometric composition with a uniform particle shape.
This method is widely used in laboratories to synthesize powders of standard composition. However, the raw material alkoxide is extremely expensive, it is impossible to synthesize an organic solvent-soluble alkoxide depending on the metal species, or there are many points such as lead alkoxide that is extremely harmful, Not an industrial method. Also, alkoxides are very sensitive to moisture and are therefore very difficult to handle. In order to carry out the reaction, it is necessary to consider a device considering the humidity in the atmosphere, which makes the device itself expensive.
【0006】[0006]
【課題を解決するための手段】本発明者らは、上記課題
を解決するために鋭意研究した結果、原料化合物、酒石
酸および過酸化水素を含有する酸性の前駆体溶液を熱処
理することにより、表面活性が高く、かつ易焼結性の複
合ペロブスカイト型酸化物が経済的に得られることを見
いだし、本発明を完成させるに至った。Means for Solving the Problems As a result of intensive research for solving the above-mentioned problems, the present inventors have found that the surface of a surface of a precursor compound is treated by heat-treating an acidic precursor solution containing a raw material compound, tartaric acid and hydrogen peroxide. The inventors have found that a highly active and easily sinterable composite perovskite type oxide can be economically obtained, and have completed the present invention.
【0007】すなわち、本発明は、鉛化合物、Me化合
物(Meは2価の金属群から選ばれる少なくとも一種の
金属元素である)、チタン化合物、ジルコニウム化合
物、ニオブ化合物、酒石酸および過酸化水素を含有する
酸性の前駆体溶液を熱処理することを特徴とする、一般
式:Pb(Me1/3Nb2/3)O3−Pb(ZrxTi1-x)O3(式
中、Meは2価の金属群から選ばれる少なくとも一種の
金属元素である。又xの範囲は0≦x≦1である。)で表
される複合ペロブスカイト型酸化物粉体の製造方法を提
供するものである。That is, the present invention contains a lead compound, a Me compound (Me is at least one metal element selected from the group of divalent metals), a titanium compound, a zirconium compound, a niobium compound, tartaric acid and hydrogen peroxide. A general formula: Pb (Me 1/3 Nb 2/3 ) O 3 -Pb (ZrxTi 1- x) O 3 (wherein Me is divalent) The present invention provides a method for producing a composite perovskite type oxide powder represented by the formula: at least one metal element selected from the metal group, and the range of x is 0 ≦ x ≦ 1.
【0008】本発明で用いる鉛化合物としては酢酸鉛、
硝酸鉛、炭酸鉛、塩基性炭酸鉛、塩基性酢酸鉛、水酸化
鉛、酸化鉛等を用いることができる。チタン化合物とし
ては四塩化チタン、オキシ硝酸チタニール及びチタンイ
ソプロポキシド等を用いることができる。ジルコニウム
化合物としてオキシ硝酸ジルコニウム、塩化ジルコニウ
ム、オキシ酢酸ジルコニウム、水酸化ジルコニウム、炭
酸ジルコニウム、硝酸ジルコニウム等を用いることがで
きる。ニオブ化合物として水酸化ニオブ、酸化ニオブを
用いることができる。Me化合物としては、Meで表され
る2価の金属群から選ばれる少なくとも一種の金属元素
の酢酸塩、特に塩基性酢酸塩(例、塩基性酢酸亜鉛)、
塩化物、硝酸塩、炭酸塩、特に塩基性炭酸塩(例、塩基
性炭酸亜鉛、塩基性炭酸ニッケル、塩基性炭酸マグネシ
ウム)等の安価な化合物を用いることができる。Me
は、好ましくは、Mg、Ni、ZnおよびCoからなる2価
の金属群から選ばれる。The lead compound used in the present invention is lead acetate,
Lead nitrate, lead carbonate, basic lead carbonate, basic lead acetate, lead hydroxide, lead oxide and the like can be used. As the titanium compound, titanium tetrachloride, titanyl oxynitrate, titanium isopropoxide and the like can be used. As the zirconium compound, zirconium oxynitrate, zirconium chloride, zirconium oxyacetate, zirconium hydroxide, zirconium carbonate, zirconium nitrate or the like can be used. As the niobium compound, niobium hydroxide or niobium oxide can be used. As the Me compound, an acetate salt of at least one metal element selected from the group of divalent metals represented by Me, particularly a basic acetate salt (eg, basic zinc acetate),
Inexpensive compounds such as chlorides, nitrates, carbonates, especially basic carbonates (eg basic zinc carbonate, basic nickel carbonate, basic magnesium carbonate) can be used. Me
Is preferably selected from the group of divalent metals consisting of Mg, Ni, Zn and Co.
【0009】本発明においては、各原料化合物は、所望
の複合ペロブスカイト型酸化物粉体の組成に対応した割
合で使用する。酒石酸は、通常、複合ペロブスカイト化
合物を構成するTi、Nbの合計モル数に対して1〜3倍
モル数を用いる。好ましくは、1.5〜2倍モルが適切
である。過酸化水素水は、通常、Ti、ZrおよびNbの
合計モル数に対して4〜8モル倍数を用いる。好ましく
は、5〜6倍が適切である。前駆体溶液の溶媒として
は、純水が用いられる。この他、エタノール、メタノー
ル等の有機系溶媒を含有させたものが使用できる。前駆
体溶液のpHは、通常、3以下となるように調整する。
このpHの調整には、例えば硝酸、酢酸、塩酸等が、好
ましくは硝酸が使用される。In the present invention, each raw material compound is used in a proportion corresponding to the desired composition of the composite perovskite type oxide powder. Tartaric acid is usually used in a molar amount of 1 to 3 times the total molar number of Ti and Nb constituting the composite perovskite compound. Preferably, a molar amount of 1.5 to 2 is suitable. The hydrogen peroxide solution is usually used in a molar ratio of 4 to 8 with respect to the total molar number of Ti, Zr and Nb. Preferably, 5 to 6 times is appropriate. Pure water is used as the solvent of the precursor solution. Besides, those containing organic solvents such as ethanol and methanol can be used. The pH of the precursor solution is usually adjusted to 3 or less.
For adjusting the pH, nitric acid, acetic acid, hydrochloric acid or the like is used, and preferably nitric acid is used.
【0010】前駆体溶液の熱処理は、好ましくは650
〜750℃で行う。熱処理は、好ましくは、前駆体溶液
を二流体ノズルより650〜750℃に加熱された加熱
筒へ霧状に吹き込み熱分解することにより行う。あるい
は、前駆体溶液を二流体ノズルあるいはアトマイズ法に
より100〜200℃に加熱された加熱筒へ霧状に吹き
込み乾燥微粒体を得、この微粒体を650〜750℃で
仮焼して行ってもよい。また、使用目的に合った粉末特
性にするために、得られた複合ペロブスカイト型酸化物
をさらに二次熱処理してもよい。また、特に原料として
使用するPb以外の化合物の少なくとも一種が塩化物の
場合、例えばNiCl2、ZnCl2を用いる場合、前駆体溶
液の温度を40〜60℃に加温した状態で用いることが
好ましい。The heat treatment of the precursor solution is preferably 650.
Perform at ~ 750 ° C. The heat treatment is preferably carried out by blowing the precursor solution into a heating cylinder heated to 650 to 750 ° C. in a mist form from a two-fluid nozzle and thermally decomposing it. Alternatively, the precursor solution may be atomized by a two-fluid nozzle or an atomizing method into a heating cylinder heated to 100 to 200 ° C. to obtain dry fine particles, and the fine particles may be calcined at 650 to 750 ° C. Good. Further, the obtained composite perovskite type oxide may be further subjected to a secondary heat treatment in order to obtain powder characteristics suitable for the purpose of use. Further, particularly when at least one compound other than Pb used as a raw material is a chloride, for example, when NiCl 2 and ZnCl 2 are used, it is preferable to use the precursor solution in a state of being heated to 40 to 60 ° C. .
【0011】[0011]
【実施例】以下、実施例および比較例により本発明をさ
らに詳しく説明するが、本発明はこれらに限定されるわ
けではない。実施例1
硝酸鉛0.2molを純水200ccに溶解し、酢酸ニッケル
0.0266molを純水100ccに溶解し、オキシ硝酸ジ
ルコニウム0.073molを純水100ccに溶解し、チタ
ンイソプロポキシド0.047molを過酸化水素水(濃度
30%)溶液6.5ccを含む硝酸酸性溶液150cc中に添
加して安定な錯体溶液を調製し、更に水酸化ニオブ0.
05332mol、酒石酸0.15mol、過酸化水素水溶液
42cc及び純水100ccを加えて安定な過ニオブ酸の錯
体溶液を調製する。調製した上記の各々の元素の溶液を
混合し、さらに純水を加えて1000ccとして透明な橙
赤色の前駆体溶液を調製した。この前駆体溶液を700
℃に調製された縦型熱分解炉中へ1時間当たり1200
ccの速度で霧状に吹き込み熱分解を行い目的の複合ペロ
ブスカイト型酸化物粉体を得た。縦型熱分解炉へ吹き込
まれた後、700℃のゾーンでの滞留時間は約1分間で
ある。得られた酸化物粉体のXRD分析及び比表面積
(SS)測定を実施した。XRD分析結果からペロスカイ
ト生成率とパイロクロア生成率を計算した。分析結果に
ついては図1及び表1に示した。EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Example 1 0.2 mol of lead nitrate was dissolved in 200 cc of pure water, 0.0266 mol of nickel acetate was dissolved in 100 cc of pure water, 0.073 mol of zirconium oxynitrate was dissolved in 100 cc of pure water, and titanium isopropoxide was 0.047 mol. Was added to 150 cc of nitric acid acidic solution containing 6.5 cc of hydrogen peroxide solution (concentration of 30%) to prepare a stable complex solution, and then niobium hydroxide of 0.
A stable complex solution of perniobic acid is prepared by adding 05332 mol, 0.15 mol of tartaric acid, 42 cc of hydrogen peroxide solution and 100 cc of pure water. The prepared solutions of each of the above elements were mixed, and pure water was added to 1000 cc to prepare a transparent orange-red precursor solution. This precursor solution is 700
1200 hours per hour into a vertical pyrolysis furnace prepared at ℃
The target composite perovskite type oxide powder was obtained by spraying in a mist at a speed of cc and conducting thermal decomposition. After being blown into the vertical pyrolysis furnace, the residence time in the 700 ° C. zone is about 1 minute. XRD analysis and specific surface area of the obtained oxide powder
(SS) measurement was performed. From the XRD analysis results, the perovskite production rate and the pyrochlore production rate were calculated. The analysis results are shown in FIG. 1 and Table 1.
【0012】比較例1
実施例と同じ組成になる様に、酸化鉛、酸化チタン、酸
化ジルコニウム、酸化ニッケル及び酸化ニオブを正確に
秤量し、混合粉砕して700℃で10分間仮焼して目的
の複合ペロブスカイト型酸化物粉体を得た。実施例と同
様に分析を実施した。図2及び表1に結果を示した。 Comparative Example 1 Lead oxide, titanium oxide, zirconium oxide, nickel oxide and niobium oxide were accurately weighed, mixed and ground, and calcined at 700 ° C. for 10 minutes so that the composition was the same as that of the example. A composite perovskite type oxide powder of was obtained. Analysis was performed as in the example. The results are shown in FIG. 2 and Table 1.
【0013】[0013]
【表1】 [Table 1]
【0014】表1及び図1、2の結果から明らかな様
に、本発明の方法で合成された複合ペロブスカイト型酸
化物は従来法で合成された粉体よりもペロブスカイト生
成率も高く微細で表面活性の高い粉体であることは明白
である。従来法では700℃での加熱時間が10分間も
あるにも拘わらず反応が進行しておらず、酸化鉛、酸化
チタン、酸化ジルコニウムの出発原料がそのまま残って
いる。それに対して本発明の方法では700℃での加熱
時間が1分間と非常に短いにも拘わらず反応進行率は9
0%と反応性の高い方法であることは明白である。As is clear from the results shown in Table 1 and FIGS. 1 and 2, the composite perovskite type oxide synthesized by the method of the present invention has a higher perovskite generation rate than the powder synthesized by the conventional method and has a fine surface. Clearly, it is a highly active powder. In the conventional method, the reaction did not proceed even though the heating time at 700 ° C. was 10 minutes, and the starting materials of lead oxide, titanium oxide, and zirconium oxide remained as they were. On the other hand, in the method of the present invention, the reaction progress rate is 9 even though the heating time at 700 ° C. is as short as 1 minute.
It is obvious that the method is highly reactive with 0%.
【0015】[0015]
【発明の効果】酸化物固相法に於ける構成元素の分散性
は言うに及ばず、共沈法に於いては構成元素の全てが瞬
間的同時に生成せず生成pH領域の低いものから順に沈
澱して行くので原子レベルでの均一分散に問題が残って
いたが、本発明では複合ペロブスカイト型酸化物を構成
する元素を全てイオンの形で均一にイオンレベルで分散
した混合溶液を調製し、噴霧焙焼或いは噴霧乾燥法によ
り直接瞬間的に固形化する為全ての元素を分子レベルで
均一に分散させることを可能とし、構成元素の均一分散
の問題を解決している。また、Tiイオンは非常に不安
定で特に加温状態(50〜60℃)では加水分解を起こし
酸化チタンとなり沈澱する性質があるが、本発明では過
酸化水素及び酒石酸の共存で安定な錯体を形成させ加温
状態でも加水分解を起こさず安定にイオンとして存在さ
せて均一分散混合溶液の状態を維持させている。また、
Nbも安定な溶液状態で存在する化合物がないが、これ
についても酒石酸と過酸化水素を共存させることによ
り、過酸化ニオブ酸イオンの状態で安定に存在させるこ
とを可能とした。よって、問題となる不安定元素のT
i、Nbを含め構成元素全ての溶液化が可能となって、構
成元素全てが分子レベルで均一分散状態を維持させるこ
とを可能とした。一方、沈澱法に於ける洗浄工程では沈
澱の溶解による組成ズレの問題があるが、本方法では噴
霧焙焼、噴霧乾燥法を用いており溶解による損失がない
ので仕込通りの組成の複合ペロブスカイト型酸化物粉体
を得ることを可能としている。さらに、本発明は、沈澱
法に必要な反応後の廃液の中和処理或いはBOD対策の
為の暴気処理が全く必要がないのでこれら公害対策費用
がいらずコストの低減をはかることが出来る。The dispersibility of the constituent elements in the oxide solid phase method is not limited to the above, and in the coprecipitation method, all of the constituent elements are not generated instantaneously at the same time, but in order of decreasing pH region. Since there is a problem of uniform dispersion at the atomic level because it precipitates, in the present invention, a mixed solution in which all the elements constituting the complex perovskite type oxide are uniformly dispersed at the ion level in the form of ions, Since it is instantly solidified directly by spray roasting or spray drying, all elements can be uniformly dispersed at the molecular level, and the problem of uniform dispersion of constituent elements is solved. Further, the Ti ion is very unstable and has a property of hydrolyzing to form titanium oxide and precipitate in the heated state (50 to 60 ° C.). However, in the present invention, a stable complex is formed in the coexistence of hydrogen peroxide and tartaric acid. Even if it is formed and heated, it does not cause hydrolysis and is stably present as ions to maintain the state of the uniformly dispersed mixed solution. Also,
Nb does not exist in a stable solution state, but coexistence of tartaric acid and hydrogen peroxide made it possible to make Nb stable in the state of niobate peroxide ion. Therefore, T of the unstable element in question
All the constituent elements including i and Nb can be solubilized, and all the constituent elements can be maintained in a uniformly dispersed state at the molecular level. On the other hand, in the washing process in the precipitation method, there is a problem of composition deviation due to dissolution of the precipitate, but in this method spray roasting and spray drying methods are used and there is no loss due to dissolution, so there is no loss due to dissolution It is possible to obtain oxide powder. Further, the present invention does not require neutralization treatment of the waste liquid after the reaction necessary for the precipitation method or aerobic treatment for BOD countermeasures, so that the cost for these pollution countermeasures is not required and the cost can be reduced.
【0016】また、アルコキシド、アセチルアセトネー
トの様な高価な有機金属化合物を用いないので安価に目
的の複合ペロブスカイト型酸化物粉体を製造することが
できる。さらに、本発明では噴霧焙焼で熱分解反応を行
わせているので噴霧された小滴の1/2以下の粒径で且
つ熱分解時のセルフブレークダウンによる微細化が相乗
作用として働き結果として非常に微細な複合ペロブスカ
イト型酸化物粉体を得ることを可能にした。そのため従
来方法の微細化の為の粉砕工程が不要である。よって、
従来法の粉砕工程から来る不純物混入問題を解決してい
る。以上の説明から明らかなように、本発明によれば、
微細で易焼結性で表面活性が高い複合ペロブスカイト型
酸化物粉体の経済的な製造方法が提供される。Further, since an expensive organometallic compound such as alkoxide or acetylacetonate is not used, the desired composite perovskite type oxide powder can be produced at low cost. Further, in the present invention, since the thermal decomposition reaction is carried out by spray roasting, the particle size is 1/2 or less of the sprayed droplets, and the miniaturization by self-breakdown during thermal decomposition works as a synergistic effect. It has made it possible to obtain extremely fine composite perovskite oxide powder. Therefore, the pulverization step for miniaturization of the conventional method is unnecessary. Therefore,
It solves the problem of impurities coming from the conventional grinding process. As is clear from the above description, according to the present invention,
Provided is an economical method for producing a complex perovskite type oxide powder which is fine, easily sinterable and has high surface activity.
【図1】 本発明の方法で合成された酸化物粉体のXR
D分析結果を示す。FIG. 1 is an XR of an oxide powder synthesized by the method of the present invention.
D shows the analysis results.
【図2】 従来の方法で合成された酸化物粉体のXRD
分析結果を示す。FIG. 2 XRD of oxide powder synthesized by conventional method
The analysis results are shown.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平3−199123(JP,A) 特開 平2−307825(JP,A) 国際公開91/002697(WO,A1) (58)調査した分野(Int.Cl.7,DB名) C01G 1/00 - 57/00 C04B 35/626 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-3-199123 (JP, A) JP-A-2-307825 (JP, A) International publication 91/002697 (WO, A1) (58) Fields investigated (Int.Cl. 7 , DB name) C01G 1/00-57/00 C04B 35/626
Claims (7)
群から選ばれる少なくとも一種の金属元素である)、チ
タン化合物、ジルコニウム化合物、ニオブ化合物、酒石
酸および過酸化水素を含有する酸性の前駆体溶液を熱処
理することを特徴とする、一般式:Pb(Me1/3Nb2/3)
O3−Pb(ZrxTi1-x)O3(式中、Meは2価の金属群か
ら選ばれる少なくとも一種の金属元素である。又xの範
囲は0≦x≦1である。)で表される複合ペロブスカイ
ト型酸化物粉体の製造方法。1. An acidic precursor containing a lead compound, a Me compound (Me is at least one metal element selected from a divalent metal group), a titanium compound, a zirconium compound, a niobium compound, tartaric acid and hydrogen peroxide. General formula: Pb (Me 1/3 Nb 2/3 ) characterized by heat-treating body solution
O 3 -Pb (ZrxTi 1- x) O 3 (in the formula, Me is at least one metal element selected from the group of divalent metals, and the range of x is 0 ≦ x ≦ 1). Method for producing composite perovskite type oxide powder.
ル、亜鉛およびコバルトよりなる請求項1記載の製造方
法。2. The method according to claim 1, wherein the divalent metal group comprises magnesium, nickel, zinc and cobalt.
求項1記載の製造方法。3. The manufacturing method according to claim 1, wherein the heat treatment temperature is 650 to 750 ° C.
製造方法。4. The method according to claim 1, wherein the pyrolysis is performed by spray roasting.
750℃に加熱された加熱筒へ霧状に吹き込み熱分解さ
せる請求項4記載の製造方法。5. The precursor solution is supplied from a two-fluid nozzle at 650 to 650.
The manufacturing method according to claim 4, wherein the powder is blown in a mist into a heating cylinder heated to 750 ° C. for thermal decomposition.
る請求項1記載の製造方法。6. The method according to claim 1, wherein the precursor solution is spray-dried and then calcined.
マイズ法により100〜200℃に加熱された加温筒へ
霧状に吹き込み乾燥微粒体を得、この微粒体を650〜
750℃で仮焼する請求項6記載の製造方法。7. The precursor solution is sprayed into a heating cylinder heated to 100 to 200 ° C. in a mist state by a two-fluid nozzle method or an atomizing method to obtain dried fine particles, and the fine particles are heated to 650 to 650.
The manufacturing method according to claim 6, wherein calcination is performed at 750 ° C.
Priority Applications (1)
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JP13592893A JP3412186B2 (en) | 1993-06-07 | 1993-06-07 | Preparation of composite perovskite oxide powder |
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JP13592893A JP3412186B2 (en) | 1993-06-07 | 1993-06-07 | Preparation of composite perovskite oxide powder |
Publications (2)
Publication Number | Publication Date |
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JPH06345435A JPH06345435A (en) | 1994-12-20 |
JP3412186B2 true JP3412186B2 (en) | 2003-06-03 |
Family
ID=15163131
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JP13592893A Expired - Lifetime JP3412186B2 (en) | 1993-06-07 | 1993-06-07 | Preparation of composite perovskite oxide powder |
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JP (1) | JP3412186B2 (en) |
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1993
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