JPH06345520A - Production of multiple oxide - Google Patents
Production of multiple oxideInfo
- Publication number
- JPH06345520A JPH06345520A JP5131854A JP13185493A JPH06345520A JP H06345520 A JPH06345520 A JP H06345520A JP 5131854 A JP5131854 A JP 5131854A JP 13185493 A JP13185493 A JP 13185493A JP H06345520 A JPH06345520 A JP H06345520A
- Authority
- JP
- Japan
- Prior art keywords
- powder
- perovskite
- peroxide
- production
- multiple oxide
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 17
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 150000002978 peroxides Chemical class 0.000 claims abstract description 6
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 13
- 239000000843 powder Substances 0.000 abstract description 27
- 238000000034 method Methods 0.000 abstract description 23
- 239000002131 composite material Substances 0.000 abstract description 12
- 150000001875 compounds Chemical class 0.000 abstract description 9
- 238000003746 solid phase reaction Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 239000000470 constituent Substances 0.000 abstract description 3
- 239000007787 solid Substances 0.000 abstract 1
- 239000007790 solid phase Substances 0.000 abstract 1
- 150000004703 alkoxides Chemical class 0.000 description 6
- 238000007796 conventional method Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000007858 starting material Substances 0.000 description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 229910052712 strontium Inorganic materials 0.000 description 3
- 239000002887 superconductor Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 150000004974 alkaline earth metal peroxides Chemical class 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- XXQBEVHPUKOQEO-UHFFFAOYSA-N potassium superoxide Chemical compound [K+].[K+].[O-][O-] XXQBEVHPUKOQEO-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000004343 Calcium peroxide Substances 0.000 description 1
- 229910002480 Cu-O Inorganic materials 0.000 description 1
- SPAGIJMPHSUYSE-UHFFFAOYSA-N Magnesium peroxide Chemical compound [Mg+2].[O-][O-] SPAGIJMPHSUYSE-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910002367 SrTiO Inorganic materials 0.000 description 1
- 229910052768 actinide Inorganic materials 0.000 description 1
- 150000001255 actinides Chemical class 0.000 description 1
- -1 alkaline earth metal alkoxides Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- ZJRXSAYFZMGQFP-UHFFFAOYSA-N barium peroxide Chemical compound [Ba+2].[O-][O-] ZJRXSAYFZMGQFP-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- LHJQIRIGXXHNLA-UHFFFAOYSA-N calcium peroxide Chemical compound [Ca+2].[O-][O-] LHJQIRIGXXHNLA-UHFFFAOYSA-N 0.000 description 1
- 235000019402 calcium peroxide Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- HPGPEWYJWRWDTP-UHFFFAOYSA-N lithium peroxide Chemical compound [Li+].[Li+].[O-][O-] HPGPEWYJWRWDTP-UHFFFAOYSA-N 0.000 description 1
- 238000009766 low-temperature sintering Methods 0.000 description 1
- 229960004995 magnesium peroxide Drugs 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000004972 metal peroxides Chemical class 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- UHCGLDSRFKGERO-UHFFFAOYSA-N strontium peroxide Chemical compound [Sr+2].[O-][O-] UHCGLDSRFKGERO-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000003826 uniaxial pressing Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Ceramic Capacitors (AREA)
- Inorganic Insulating Materials (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は、圧電素子、誘電体等の
電子材料として使用されるペロブスカイト型複合酸化物
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 a perovskite complex oxide used as an electronic material such as a piezoelectric element and a dielectric.
【0002】[0002]
【従来の技術】従来から、複合酸化物の製造に際して
は、各成分の粉末又はその前駆体を混合し、物理的に均
一に混合された各原料を焼成により固相反応を形成せし
めることによって目的の成分組成を有する複合酸化物と
している。2. Description of the Related Art Conventionally, in the production of composite oxides, the powder of each component or its precursor is mixed, and the physically homogeneously mixed raw materials are baked to form a solid-phase reaction. A composite oxide having the component composition of
【0003】しかし、このような固相反応による調製に
おいては、その反応の進行が緩慢であるため、各成分の
粉末を混合して焼成する方法では、各成分の反応のため
に高温が必要であり、得られた粉末は粒成長を生じ易く
微細化が困難であり、且つ固相反応の際には各成分相互
の完全な反応は困難である。このようにして得られた粉
末は、通常、活性が低く焼結体を得るためには高温での
焼成や焼結助剤の添加が必要である。したがって、目的
とする化学組成への制御が難しく、得られる製品の特性
も劣ったものとなる。However, in the preparation by such a solid phase reaction, the progress of the reaction is slow, so that the method of mixing powders of the respective components and firing the mixture requires a high temperature for the reaction of the respective components. However, the obtained powder easily causes grain growth and is difficult to be made fine, and it is difficult to completely react each component with each other in the solid phase reaction. The powder thus obtained usually has low activity and requires firing at a high temperature and addition of a sintering aid in order to obtain a sintered body. Therefore, it is difficult to control the desired chemical composition, and the properties of the obtained product are inferior.
【0004】また、成分が均一に分散し、より微細な粉
末を得るために、湿式共沈法や金属アルコキシドを出発
原料とした製造方法が試みられている。Further, in order to obtain a finer powder in which the components are uniformly dispersed, a wet coprecipitation method or a production method using a metal alkoxide as a starting material has been tried.
【0005】例えば、「ジャーナル・アメリカン・セラ
ミック・ソサイアティー(J.Am.Ceram.So
c.)1966年発行、291、49」や、同じく、
「1969年発行、523、52」、さらには、同じ
く、「1970年発行、53、91」には、BaTiO
3 やSrTiO3 の組成のずれのない微細粒子製造に、
金属アルコキシドを用いた製造が可能であることが報告
されている。For example, "Journal American Ceramic Society (J. Am. Ceram. So
c. ), Issued 1966, 291, 49 ",
In "1969, 523, 52", and also in "1970, 53, 91," BaTiO
For the production of fine particles without deviation of the composition of 3 and SrTiO 3 .
It has been reported that production using a metal alkoxide is possible.
【0006】しかしながら、湿式共沈法では、多成分を
同時に沈殿させるための条件設定が難しく、特に、Mg
等のアルカリ土類金属やZn等の遷移金属は単なるpH
の調製のみでは沈殿し難い。結果として、得られる複合
酸化物前駆体の組成が目的の組成からずれ、最終製品で
あるセラミックス等の特性を悪くしてしまう。However, in the wet coprecipitation method, it is difficult to set the conditions for precipitating multiple components at the same time.
Alkaline earth metals such as Zn and transition metals such as Zn are simply pH
It is difficult to precipitate only by preparing. As a result, the composition of the obtained composite oxide precursor deviates from the intended composition, and the characteristics of the final product such as ceramics are deteriorated.
【0007】また、金属アルコキシド法においては、出
発原料である金属アルコキシドは、Si等の一部の元素
を除き、高価であるため大量に用いることは現実的では
ない。また、金属アルコキシドの有機溶剤への溶解度が
小さいものが多く、加水分解のための均一な溶液を調製
するため多量の溶剤の使用や各種有機溶剤の組み合せを
検討する必要があり、製造に必要な容積がかなり大きく
なる。操作上の問題点として、金属アルコキシドが水に
対して不安定であるため、水分を含まない雰囲気中で取
り扱う必要がある。特に、アルカリ金属やアルカリ土類
金属のアルコキシドは、炭酸ガスが共存すると得られた
加水分解生成物が炭酸塩となるため、添加する水の脱炭
酸を併せて行う必要があり、とくに、複合ペロブスカイ
ト型の複合酸化物の製造に適用した場合には、その調整
操作が難しいという問題がある。Further, in the metal alkoxide method, the metal alkoxide as a starting material is expensive except for some elements such as Si and is not practical to use in large quantities. Also, many of the metal alkoxides have low solubility in organic solvents, and it is necessary to study the use of large amounts of solvents and combinations of various organic solvents in order to prepare a uniform solution for hydrolysis, which is necessary for production. The volume is quite large. As a problem in operation, since metal alkoxide is unstable to water, it is necessary to handle it in an atmosphere containing no water. In particular, for alkali metal and alkaline earth metal alkoxides, the hydrolysis product obtained when carbon dioxide gas coexists forms a carbonate, so it is necessary to decarboxylate the water to be added. When it is applied to the production of a type of complex oxide, there is a problem that its adjusting operation is difficult.
【0008】また、複合ペロブスカイト粉末の合成法と
して、特開昭58−199716号公報には、金属酸化
物のペロブスカイト型化合物として、単体で圧電セラミ
ックス材料、誘電体セラミックス材料として、AをB
a,Sr,Ca,Pbから選ばれた元素とし、Bを希土
類元素,アクチノイド,Fe,Co,Mn,Ni,R
h,In,Ga,V,Cr,Al,Zn,Mgの中から
選ばれた元素、B2 をNb,Sb,あるいはTaとし
て、A(B1 1/3B2 2/3)O3 構造を持つ三成分
系以上の複合ペロブスカイト粉末を低温で合成すること
が開示されている。Further, as a method for synthesizing a composite perovskite powder, Japanese Patent Laid-Open No. 58-199716 discloses a perovskite type compound of a metal oxide, a piezoelectric ceramic material and a dielectric ceramic material as A alone, and A as B.
a, Sr, Ca, Pb as an element, B as a rare earth element, actinide, Fe, Co, Mn, Ni, R
An element selected from h, In, Ga, V, Cr, Al, Zn, and Mg, and B 2 as Nb, Sb, or Ta, have an A (B 1 1 / 3B 2 2/3) O 3 structure. It is disclosed to synthesize a composite perovskite powder having three or more components at a low temperature.
【0009】また、特開昭62−87456号公報に
は、予め合成されたペロブスカイト粉末にアルカリ土類
金属の過酸化物を添加することで、還元雰囲気下での酸
素分圧の制御を可能とした卑金属電極と同時に焼成でき
ることが開示されている。Further, in Japanese Patent Laid-Open No. 62-87456, it is possible to control the oxygen partial pressure in a reducing atmosphere by adding a peroxide of an alkaline earth metal to a pre-synthesized perovskite powder. It is disclosed that the base metal electrode can be fired at the same time.
【0010】さらに、特開昭63−297262号公報
には、SEを希土類金属、EAをアルカリ土類金属とし
たとき、SE−EA−Cu−Oの酸化物超電導体を、化
学的に且つ物理的に閉じた高圧容器内で製造するに当た
って、熱分解性のアルカリ土類金属過酸化物を酸素分圧
の調整のために添加することで、超電導体の特定の共存
相の組成に相当する組成を有する保護層で覆って、所望
の超電導体相を熱力学的に安定化させることが開示され
ている。Further, in Japanese Patent Application Laid-Open No. 63-297262, when SE is a rare earth metal and EA is an alkaline earth metal, an oxide superconductor of SE-EA-Cu-O is chemically and physically prepared. In the production in a closed high-pressure vessel, by adding a thermally decomposable alkaline earth metal peroxide for adjusting the oxygen partial pressure, the composition corresponding to the composition of the specific coexisting phase of the superconductor. It is disclosed that the desired superconductor phase is thermodynamically stabilized by covering it with a protective layer having.
【0011】さらに、電子通信学会材料研究会資料、C
PM86−31、p41(1986)には、Ba(Mg
1/3Nb2/3)O3 型の焼結体の作製には、急速に
成形体を加熱した炉中に装入する急速昇温法が有効であ
ることが報告されている。[0011] Furthermore, the Institute of Electronics and Communication Engineers Materials Research Materials, C
PM86-31, p41 (1986) contains Ba (Mg
It has been reported that a rapid heating method in which a compact is rapidly charged into a furnace is effective for producing a 1 / 3Nb2 / 3) O 3 type sintered body.
【0012】しかしながら、昇温法は、難焼結材料の高
密度化のために有効な方法の一つであるが、特殊な焼成
装置を必要とするため高価となり、さらには、量産化や
大型形状の製品の製造には不向きである。[0012] However, the temperature rising method is one of the effective methods for increasing the density of the difficult-to-sinter material, but it requires a special baking apparatus and is therefore expensive. It is not suitable for manufacturing shaped products.
【0013】ところが、上記の従来のぺロブスカイト粉
末の製造法は、工業的な生産方法として、高価な設備が
必要であったり、あるいは、大型形状の製品の製造面か
ら種々解決すべき問題がある。However, the above-mentioned conventional method for producing perovskite powder has a problem that it requires an expensive facility as an industrial production method, or various problems to be solved in terms of producing a large-sized product. .
【0014】[0014]
【発明が解決しようとする課題】本発明の目的は、ぺロ
ブスカイト型複合酸化物のより簡便な製造方法を提供す
ることにある。An object of the present invention is to provide a simpler method for producing a perovskite type composite oxide.
【0015】[0015]
【課題を解決するための手段】本発明に係るペロプスカ
イト型複合酸化物の製造は、構成する成分の一種又は一
種以上をアルカリ又はアルカリ土類金属の過酸化物とし
て用いることを特徴とする。The production of the perovskite type complex oxide according to the present invention is characterized by using one or more of the constituent components as an alkali or alkaline earth metal peroxide.
【0016】本発明は、一般に、難焼結性であるペロブ
スカイト、複合ペロブスカイト構造を有する化合物の製
造において有効である。例えば、構造式ABO3 、A
(B1l/3B2 2/3)O3 、A(B3 2/3B4 1
/3)O3 、A(B5 l/2B6 l/2)O3 で表わさ
れる化合物やこれらの固溶体である。AはBa,Sr,
Ca,Mg,Li等がある。BはTi,Zr,Sn等が
ある。B1 はMg,Ca,Sr,Ba,Ni,Zn,C
o等がある。B2 はTa,Nb,V,Sb等がある。B
3 とB5 はFe等がある。B4 はW等がある。B6 はN
b等がある。これらの元素はアルカリ土類金属を除き、
酸化物として用いられる。The present invention is generally effective in the production of a compound having a perovskite or complex perovskite structure which is difficult to sinter. For example, the structural formula ABO 3 , A
(B 1 l / 3B 2 2/3) O 3 , A (B 3 2 / 3B 4 1
/ 3) O 3 and compounds represented by A (B 5 1 / 2B 6 1/2) O 3 and solid solutions thereof. A is Ba, Sr,
There are Ca, Mg, Li and the like. B includes Ti, Zr, Sn and the like. B 1 is Mg, Ca, Sr, Ba, Ni, Zn, C
There are o etc. B 2 includes Ta, Nb, V, Sb and the like. B
3 and B 5 have Fe and the like. B 4 has W etc. B 6 is N
b etc. These elements exclude alkaline earth metals,
Used as an oxide.
【0017】Aサイトの構成元素であるアルカリ又はア
ルカリ土類金属は過酸化物の形で使用される。例えば、
過酸化リチウム,過酸化ナトリウム,過酸化カリウム等
のアルカリ金属や過酸化マグネシウム、過酸化カルシウ
ム、過酸化ストロンチウム、過酸化バリウム等のアルカ
リ土類金属の過酸化物がある。Bサイトにこれら元素を
含むぺロブスカイト化合物である場合も、使用すること
が可能である。The alkali or alkaline earth metal which is a constituent element of the A site is used in the form of peroxide. For example,
There are peroxides of alkali metals such as lithium peroxide, sodium peroxide and potassium peroxide, and alkaline earth metal peroxides such as magnesium peroxide, calcium peroxide, strontium peroxide and barium peroxide. A perovskite compound containing these elements at the B site can also be used.
【0018】一種又は一種以上の過酸化物を含む混合粉
末を、加熱処理することにより目的の複合酸化物が得ら
れる。加熱処理温度は個々の化合物により適性温度が異
るため、個別に設定される。得られた粉末は、有機結合
材等と混ぜた後、公知の方法で目的とする形状に成形さ
れる。例えば、1軸プレス法,CIP法,鋳込法,射出
法,ドクターブレード法等で各種形状の成形体が得られ
る。成形体は、目的や組成に応じて、酸化雰囲気、非酸
化雰囲気で焼成される。焼成温度は組成により個別に決
定される。By heating the mixed powder containing one or more peroxides, the desired composite oxide can be obtained. The heat treatment temperature is set individually because the suitable temperature varies depending on the individual compound. The obtained powder is mixed with an organic binder or the like and then molded into a desired shape by a known method. For example, molded articles of various shapes can be obtained by the uniaxial pressing method, CIP method, casting method, injection method, doctor blade method or the like. The molded body is fired in an oxidizing atmosphere or a non-oxidizing atmosphere depending on the purpose and composition. The firing temperature is individually determined by the composition.
【0019】[0019]
【作用】本発明において使用されるアルカリ金属又はア
ルカリ土類金属の過酸化物の作用については、必ずしも
明確に解明されたものではないが、以下の作用を奏する
ものと考えられる。The action of the alkali metal or alkaline earth metal peroxide used in the present invention has not been clearly clarified, but it is considered to have the following action.
【0020】アルカリ金属又はアルカリ土類金属の過酸
化物は、1000℃以下の低温で溶融、分解し微細な酸
化物を生成し、これによって、生成する融液や微細な粒
子が他の成分中に均一に浸透、分散することが可能とな
り、より低温で均一な複合酸化物が生成すると考えられ
る。通常の固相法より微細で、活性の高い複合酸化物粉
末が得られるため、炭酸塩を用いる既に公知の通常の固
相反応法より低温でペロブスカイト化合物が製造可能と
なる。また、得られる粉末は従来法に比べ熱履歴が少な
くより高い表面活性を有するため、低温焼結が可能にな
る。Alkali metal or alkaline earth metal peroxides are melted and decomposed at a low temperature of 1000 ° C. or less to form fine oxides. As a result, the resulting melt or fine particles are mixed with other components. Therefore, it is considered that the compound oxide can be uniformly permeated and dispersed, and a uniform composite oxide is generated at a lower temperature. Since a complex oxide powder finer and more active than the ordinary solid-phase method can be obtained, the perovskite compound can be produced at a lower temperature than the already known ordinary solid-phase reaction method using a carbonate. Further, the obtained powder has less heat history and higher surface activity as compared with the conventional method, and thus low temperature sintering becomes possible.
【0021】[0021]
【実施例】本発明の実施例として、出発原料、生成温
度、得られた粉末の比表面積、目的の複合酸化物を表l
にまとめた。Examples As examples of the present invention, starting materials, formation temperatures, specific surface areas of the obtained powders, and target complex oxides are shown in Table 1.
Summarized in.
【0022】同表1に示すそれぞれの出発原料として、
アルカリ又はアルカリ土類金属の過酸化物として、B4
O2 ,SiO2 ,LiO2 を用い、目的の複合酸化物の
組成比になるように秤量した。この混合酸化物をメタノ
ール中で湿式混合し、乾燥し、300から1400℃の
温度で50℃刻みに大気中で2時間仮焼した。得られた
粉末の結晶相を粉末X線回折法により測定した。その結
果、目的とするぺロブスカイト化合物が得られたことが
わかった。As the starting materials shown in Table 1,
As an alkali or alkaline earth metal peroxide, B 4
O 2 , SiO 2 and LiO 2 were used and weighed so that the composition ratio of the target composite oxide was obtained. The mixed oxide was wet-mixed in methanol, dried, and calcined at a temperature of 300 to 1400 ° C. in steps of 50 ° C. in the atmosphere for 2 hours. The crystal phase of the obtained powder was measured by the powder X-ray diffraction method. As a result, it was found that the target perovskite compound was obtained.
【0023】[0023]
【表1】 比較例として、同じく表1に示す炭酸塩を出発原料とし
て用い同様に複合酸化物粉末の調製を行った。[Table 1] As a comparative example, a complex oxide powder was similarly prepared using the carbonate shown in Table 1 as a starting material.
【0024】実施例1〜6に示すペロブスカイト系複合
酸化物は、Aサイト金属の過酸化物を使用することで、
通常の炭酸塩を使用した比較例1−3の場合に比べ数1
00℃の低温合成が可能となっている。製品としては、
比表面積が2.5m2 /g以上(比表面積径0.5μm
以下)の微細な粉末が得られた。The perovskite complex oxides shown in Examples 1 to 6 are prepared by using the A-site metal peroxide.
Compared to the case of Comparative Example 1-3 using ordinary carbonate, the number 1
Low temperature synthesis of 00 ° C is possible. As a product,
Specific surface area of 2.5 m 2 / g or more (specific surface area diameter 0.5 μm
The following fine powder was obtained.
【0025】実施例7,8に示すように、複合ぺロブス
カイト構造を有するBa(Mg1/3Ta2/3)O3
粉末では、比表面積径0.5μm以下の単相粉末が従来
法の比較例4、5に比べ150℃低温で合成できた。と
くに、コロンバイト法(Bサイト元素であるMgOとT
a2 O5 を予め反応させ、MgTa2 O6 を合成する。
これをAサイト元素であるBaと反応させる方法)を併
用した実施例8では、1050℃でBa(Mg1/3T
a2/3)O3 の単相粉末が得られ、より低温度の仮焼
で目的物が得られることから、より効果的であることが
わかる。コロンバイト法を併用した場合でも、比較例5
の従来法では、単相粉末を得るために1250℃の高温
が必要であり、比表面積も0.6m2 /gと小さくなっ
ていることがわかる。As shown in Examples 7 and 8, Ba (Mg1 / 3Ta2 / 3) O 3 having a composite perovskite structure.
As the powder, a single-phase powder having a specific surface area of 0.5 μm or less could be synthesized at a low temperature of 150 ° C. as compared with Comparative Examples 4 and 5 of the conventional method. In particular, the columbite method (B site elements MgO and T
a 2 O 5 is reacted in advance to synthesize MgTa 2 O 6 .
In Example 8 in which this is used together with the method of reacting it with Ba which is an A site element, Ba (Mg1 / 3T) at 1050 ° C.
Since a single-phase powder of a2 / 3) O 3 can be obtained and the target product can be obtained by calcination at a lower temperature, it can be seen that it is more effective. Comparative example 5 even when the columbite method was used together
It can be seen that the conventional method of (1) requires a high temperature of 1250 ° C. to obtain a single-phase powder, and the specific surface area is as small as 0.6 m 2 / g.
【0026】[0026]
【発明の効果】従来法に比べ低温で均一粉末が合成可能
となる。The uniform powder can be synthesized at a lower temperature than the conventional method.
【0027】結果として、得られる粉末は 低温で得ら
れるため、粒成長があまり進行していないので、粉砕が
容易であり、粉砕時の不純物の混入を最小限にすること
ができる。As a result, since the obtained powder is obtained at a low temperature, grain growth has not progressed so much, so that it is easy to pulverize and it is possible to minimize contamination of impurities during pulverization.
【0028】また、従来法に比べ表面活性が高く、焼結
性に優れたペロブスカイト型複合酸化物の粉末を低温で
得ることができる。Further, it is possible to obtain a powder of perovskite type complex oxide having a high surface activity and excellent sinterability as compared with the conventional method at a low temperature.
【0029】したがって、焼結機に際しては、焼結助材
等の第二成分の添加が不要であり、化学量論比に近い組
成の焼結体が容易に製造可能となる。Therefore, it is not necessary to add a second component such as a sintering aid in the sintering machine, and a sintered body having a composition close to the stoichiometric ratio can be easily manufactured.
Claims (1)
であって、組成成分の一種又は一種以上をアルカリ又は
アルカリ土類金属の過酸化物として用いて加熱処理する
複合酸化物の製造方法。1. A method for producing a perovskite type complex oxide, which comprises subjecting one or more of the composition components as a peroxide of an alkali or alkaline earth metal to a heat treatment, and carrying out heat treatment.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP5131854A JPH06345520A (en) | 1993-06-02 | 1993-06-02 | Production of multiple oxide |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP5131854A JPH06345520A (en) | 1993-06-02 | 1993-06-02 | Production of multiple oxide |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH06345520A true JPH06345520A (en) | 1994-12-20 |
Family
ID=15067680
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP5131854A Pending JPH06345520A (en) | 1993-06-02 | 1993-06-02 | Production of multiple oxide |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH06345520A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011195383A (en) * | 2010-03-19 | 2011-10-06 | Kyocera Corp | Piezoelectric substance and piezoelectric element using the same |
-
1993
- 1993-06-02 JP JP5131854A patent/JPH06345520A/en active Pending
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011195383A (en) * | 2010-03-19 | 2011-10-06 | Kyocera Corp | Piezoelectric substance and piezoelectric element using the same |
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