JPH0251463A - Preparation of multiple oxide ceramic - Google Patents
Preparation of multiple oxide ceramicInfo
- Publication number
- JPH0251463A JPH0251463A JP63202892A JP20289288A JPH0251463A JP H0251463 A JPH0251463 A JP H0251463A JP 63202892 A JP63202892 A JP 63202892A JP 20289288 A JP20289288 A JP 20289288A JP H0251463 A JPH0251463 A JP H0251463A
- Authority
- JP
- Japan
- Prior art keywords
- site
- metal
- oxide
- coprecipitate
- composite 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
- 239000011224 oxide ceramic Substances 0.000 title abstract 3
- 229910052574 oxide ceramic Inorganic materials 0.000 title abstract 3
- 238000002360 preparation method Methods 0.000 title abstract 2
- 150000001875 compounds Chemical class 0.000 claims abstract description 23
- 239000000843 powder Substances 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 11
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 6
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 239000007921 spray Substances 0.000 claims abstract description 5
- 150000004679 hydroxides Chemical class 0.000 claims abstract description 4
- 150000002823 nitrates Chemical class 0.000 claims abstract description 3
- 239000002131 composite material Substances 0.000 claims description 29
- 229910052573 porcelain Inorganic materials 0.000 claims description 21
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000010304 firing Methods 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 150000002736 metal compounds Chemical class 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 9
- 239000002245 particle Substances 0.000 abstract description 6
- 239000013078 crystal Substances 0.000 abstract description 5
- 238000001354 calcination Methods 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 2
- 229910021529 ammonia Inorganic materials 0.000 abstract 1
- 238000000975 co-precipitation Methods 0.000 abstract 1
- 239000002244 precipitate Substances 0.000 description 9
- 239000011777 magnesium Substances 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- WPCMRGJTLPITMF-UHFFFAOYSA-I niobium(5+);pentahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[Nb+5] WPCMRGJTLPITMF-UHFFFAOYSA-I 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- NDSXSCFKIAPKJG-UHFFFAOYSA-N CC(C)O[Ti] Chemical compound CC(C)O[Ti] NDSXSCFKIAPKJG-UHFFFAOYSA-N 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 1
- XMFOQHDPRMAJNU-UHFFFAOYSA-N lead(ii,iv) oxide Chemical compound O1[Pb]O[Pb]11O[Pb]O1 XMFOQHDPRMAJNU-UHFFFAOYSA-N 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- DQTJHJVUOOYAMD-UHFFFAOYSA-N oxotitanium(2+) dinitrate Chemical compound [O-][N+](=O)O[Ti](=O)O[N+]([O-])=O DQTJHJVUOOYAMD-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は複合酸化物磁器の製造方法、特に、誘電体磁器
、強誘電体磁器、圧電磁器など電子部品用磁器材料とし
て有用な複合酸化物磁器の製造方法に関する。Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a method for manufacturing composite oxide porcelain, and in particular to a method for manufacturing composite oxide porcelain useful as a porcelain material for electronic components such as dielectric porcelain, ferroelectric porcelain, and piezoelectric porcelain. Concerning a method of manufacturing porcelain.
（従来の技術）
従来、複合酸化物磁器の製造方法としては、複合酸化物
を構成する金属元素の酸化物や炭酸塩などの粉末を所定
の割合で混合し、その混合物を仮焼、粉砕したのち、所
定の形状に成形して焼成する粉末法が主として採用され
ている。(Prior art) Conventionally, the method for manufacturing composite oxide porcelain involves mixing powders such as oxides and carbonates of metal elements constituting the composite oxide in a predetermined ratio, and then calcining and pulverizing the mixture. Later, a powder method in which the material is molded into a predetermined shape and fired has been mainly adopted.
（発明が解決しようとする課題）
しかしながら、前記粉末法では、機械的粉砕によって生
成された原料粉末を用いているため、ミクロ的に均一に
分散した混合粉末を得ることは不可能であり、そのため
、反応し易い酸化物同士が先に反応してそれらの化合物
を形成し、その後に残りの酸化物が前記化合物と反応し
て最終生成物である複合酸化物を生成する、あるいは、
チタン酸ジルコン酸鉛（ＰＺＴ）磁器のように、焼成の
初期段階で正方晶系および斜方晶系の２相を形成し、最
終的に正方晶系または斜方晶系結晶構造の単一相となる
など２段階で反応が進行することになり、均質な磁器を
得ることが困難であった。(Problems to be Solved by the Invention) However, since the powder method uses raw material powder produced by mechanical pulverization, it is impossible to obtain a microscopically uniformly dispersed mixed powder; , Reactive oxides first react with each other to form those compounds, and then the remaining oxides react with said compounds to produce the final product, a composite oxide, or
Like lead zirconate titanate (PZT) porcelain, it forms two phases, tetragonal and orthorhombic, in the initial stage of firing, and finally forms a single phase with tetragonal or orthorhombic crystal structure. The reaction proceeded in two stages, making it difficult to obtain homogeneous porcelain.
しかも、粉体の粒径が極めて大きく、また、粒径の分布
も大きい粒度に偏っているため、粒径が大きく結晶粒子
が不均一な磁器しか得られないという問題があった。ま
た、粉体の粒子径が大きいことに起因して磁器が多数の
大きな空孔を有する他、パイロクロア化合物が生成し易
く、これを消失させろためには高温で焼成する必要があ
り、鉛などのように比較的低い温度で蒸発しやすい成分
を含む場合には組成が変動するという問題があった。Moreover, since the particle size of the powder is extremely large and the particle size distribution is biased towards large particle sizes, there is a problem in that only porcelain with large particle sizes and non-uniform crystal grains can be obtained. In addition, porcelain has many large pores due to the large particle size of the powder, and pyrochlore compounds are easily generated, which requires firing at high temperatures to eliminate them. When containing components that easily evaporate at relatively low temperatures, such as this, there is a problem that the composition fluctuates.
他方、これらの問題を解決する手段として、複合ペロブ
スカイト化合物を構成する総ての金属元素を湿式反応に
より、水酸化物などの共沈体あるいは沈澱物として析出
させ、その共沈体もしくは沈澱物を濾別後、洗浄、脱水
して焼成する方法が提案されている。しかしながら、こ
れらの共沈体もしくは沈澱物であっても、多少の溶解度
を持っているため、洗浄、脱水を反復すると、それらが
溶出する分だけ成分の損失が起こり、組成の変動が避け
られないという問題があった。しかも、Ａサイトの鉛を
Ｂサイトの成分と共沈さ仕ると、鉛が非常に蒸発し易い
ＰｂＯの形態で生成しているため、仮焼段階でｐｂか蒸
発してモル比にズレを生じるという問題もあった。On the other hand, as a means to solve these problems, all the metal elements constituting the composite perovskite compound are precipitated as coprecipitates or precipitates such as hydroxides by wet reaction, and the coprecipitates or precipitates are A method has been proposed in which the material is filtered, washed, dehydrated, and then fired. However, even these coprecipitates or precipitates have some degree of solubility, so repeated washing and dehydration will cause a loss of components due to their elution, and compositional fluctuations are unavoidable. There was a problem. Moreover, when the lead at the A site is co-precipitated with the components at the B site, the lead is generated in the form of PbO, which evaporates very easily. There were also problems that occurred.
従って、本発明は、製造時に成分の損失を生じさせるこ
となく、均一で微細な結晶粒子からなる複合酸化物磁器
を製造することができる方法を得ることを目的とする。Therefore, an object of the present invention is to obtain a method capable of producing composite oxide porcelain consisting of uniform and fine crystal grains without causing loss of components during production.
（課題を解決するための手段）
本発明は、前記課題を解決するための手段として、一般
式＋ （ＡｘＡ’ ＋−ｘ）（ＢｙＢ’ １−Ｙ）０
３（式中、ＡサイトのＡおよびＡ゛は同じ又は異なる１
価または２価の金属、ＢサイトのＢおよびＢは同じ又は
異なる２〜６価の金属を表す。）で示される複合ペロブ
スカイト型化合物からなる複合酸化物磁器の製造方法に
おいて、
前記複合ペロブスカイト型化合物のＡサイトまたはＢサ
イトの金属元素の硝酸塩および水酸化物からなる群から
選ばれた少なくとも二つの水溶性金属化合物を含む水溶
液に、アンモニア水を加えて共沈体を生成させ、該共沈
体をロータリエバボレイータもしくはスプレィドライヤ
ーで溶媒を除去したのち、得られた乾燥粉末を仮焼して
ＡサイトまたはＢサイトの金属元素の複合酸化物を生成
さけ、該ＡサイトまたはＢサイトの金属元素の複合酸化
物を、それとは別に調製されたＢサイトまたはＡサイト
の金属酸化物と精秤、混合して焼成することを特徴とす
る複合酸化物磁器の製造方法を提供するものである。(Means for Solving the Problem) The present invention provides, as a means for solving the problem, the general formula + (AxA' +-x) (ByB' 1-Y)0
3 (in the formula, A and A′ of the A site are the same or different 1
A valent or divalent metal, B and B at the B site represent the same or different divalent to hexavalent metals. ), in which at least two water-soluble porcelains selected from the group consisting of nitrates and hydroxides of metal elements at the A site or B site of the composite perovskite compound are provided. Aqueous ammonia is added to an aqueous solution containing a metal compound to form a coprecipitate, the solvent is removed from the coprecipitate using a rotary evaporator or a spray dryer, and the resulting dry powder is calcined to produce A. Precisely weigh and mix the composite oxide of the metal element at the A site or B site with the separately prepared metal oxide at the B site or A site, avoiding the generation of a composite oxide of the metal element at the site or B site. The present invention provides a method for manufacturing composite oxide porcelain, which is characterized in that the composite oxide porcelain is fired.
前記一般式で示される複合ペロブスカイト型化合物から
なる複合酸化物磁器としては、例えば、次の一般式（１
）〜（Ｖｌ）で示される！成分系、２成分系、３成分系
その他の多成分系磁器組成物が挙げられる。As a composite oxide porcelain made of a composite perovskite type compound represented by the above general formula, for example, the following general formula (1
)~(Vl)! Examples include component type, two-component type, three-component type and other multi-component type ceramic compositions.
なお、前記複合ペロブスカイト型化合物には、電気的あ
るいは機械的特性を向上させるため、主成分である複合
ペロブスカイト型化合物にＣｒ、Ｎｂ、Ｔａ、Ｂ１ＳＭ
ｎなど金属や、アルカリ土金属、あるいは希土類元素を
添加して変性したものも含まれる。In addition, in order to improve the electrical or mechanical properties of the composite perovskite type compound, Cr, Nb, Ta, B1SM, etc. are added to the composite perovskite type compound which is the main component.
It also includes those modified by adding metals such as n, alkaline earth metals, or rare earth elements.
前記複合ペロブスカイト型化合物の代表的なものとして
は、
一般式（１）： Ａ” （Ｂ” ＋７３Ｂ” ２／
３）Ｃｈで示される化合物、例えば、Ｐｂ（ＴＬ／３Ｚ
ｒ２／ ３）０３、Ｂａ（Ｚｎ＋ｚ ３Ｎｂｔ／３）０
３、Ｂａ（Ｃｄ＋ｚ ３Ｎｂｔｚ ｙ）Ｃ１＋、Ｂａ（
Ｍｇ＋／３Ｎｂ２／ ＪＯ３，５ｒ（Ｃｄ＋／３Ｎｂｔ
／３）０３％Ｐ ｂ（Ｍｇ＋／３ Ｎ ｂｔ／３）’０
３、Ｐ ｂ（Ｎ ＩＩ７３Ｎｂｔ／３）０３、Ｐ ｂ（
Ｍｎ＋ｙ ｚＮｂｔ／＊）０３、Ｐｂ（Ｍｇ＋、ｚ ３
Ｔａ、／３）０３、Ｐｂ（Ｎｌ＋７ 、Ｔａｔ／ ａ）
０３、Ｐ ｂ（Ｃｄ＋７３Ｎｂｔ７３）０３；一般式（
ＩＩ）： Ａ” （Ｂ””Ｉ／ ２Ｂ針１／２）０３
で示される化合物、例えば、
Ｂａ（Ｆ’ ｅｌｉ ｔＮｂ＋／ｚ）０３、Ｂａ（Ｓ、
ｃ＋／ｌＮｂ＋／２）０３、Ｃａ（Ｃｒ＋／ａＮｂ＋／
ＪＯ３、Ｐｂ（Ｐｅｌ／ｌＮｂ＋７２）０３、Ｐｂ（Ｐ
ｅ＋７ ｔＴａ＋ｙ ｔ）０３、Ｐｂ（Ｓｃ＋／ｌＮｂ
＋／１）Ｏｓ、Ｐｂ（Ｓｃ５ｚ ｔＴａ＋ｙ ｔ）０３
、Ｐ ｂ（Ｙ ｂ＋／ｌＮｂ＋／ｌ）０３、Ｐｂ（Ｙｂ
＋／１ＴａＩ７ ｔ）Ｏｓ、Ｐｂ（Ｌｕ＋／ｌＮｂ＋／
１）０３、Ｐｂ（Ｉｒ＋＋／、Ｎｂ、、ＪＯ３；
一般式（ＩＩＩ）： Ａ”” （Ｂ” Ｉ／ ２Ｂ”
Ｉ／ ＊）０＋で示される化合物、例えば、
Ｐｂ（Ｃｄ＋／ｌＷ１／り０３、Ｐ ｂ（Ｍｒ＋＋／ｌ
Ｗ Ｉ／ りＯｓ、Ｐｂ（ＺｎＩ７２Ｗｌ／ ＪＯ３，
Ｐｂ（Ｍｇ＋７２Ｗｌ／ ｔ）Ｏ３゜Ｐ ｂ（Ｃｏｔ／
、ｗＩ／１）０３、Ｐ ｂ（Ｎ Ｉ １／ ２Ｗ ＋／
２） ０３、Ｐｂ（Ｍｇ＋／１Ｔｅ７ ｔ）０３、Ｐ
ｂ（Ｍｎ＋／１Ｔｅ７２）０３、Ｐ ｂ（Ｃｏ＋／１Ｔ
ｅｌ／１）Ｏｓ、Ｐｂ（Ｃｕ＋７２Ｗ＋／１）０３一般
式（■）： Ａ” （Ｂ”” ２７３Ｂ” ＋／ ３
）０＊で示される化合物、例えば、Ｐｂ（Ｆｅｔ７３Ｖ
ｂ／＊）Ｏｓニ一般式（Ｖ）： Ａ” （Ｂ ｌ／
ｔ” Ｂ ｌ／ ｔ” ）０３で示される化合物、例え
ば、
Ｐｂ（Ｓｎ＋／ｌｓｂ＋／１）０３、Ｌ ａ（Ｍｇ＋／
２Ｔ Ｌ７ ｔ）０３、Ｎｄ（Ｍｇ１７ｔＴＬ７ ｔ
）Ｏｓ；及び、一般式（ＶＴ）： （Ａ” Ｉ／ ｔ
Ａ３“Ｉ／ ２）Ｂ” ０３で示される化合物、例えば
、
ＣＮａ＋ｙ ２Ｌａ＋／ＪＴｉＯ＊、（Ｋｌ／ 、Ｌａ
＋／ ｔ）Ｔｉｏｓ、（Ｎａ＋／ｌｃｅ＋７ ｔ）Ｔｉ
Ｏ＋、ＣＮａ、／ｚＮｄ＋／ｌ）Ｔ ｉｏ３、（Ｎｄ＋
／２Ｂ ｉ７ ｔ）Ｔ ｉｏ ３、（Ｋ ＋／ ｔＢ
Ｌ／ ｔ）Ｔ ｉＯ＊、などが挙げられる。A typical compound perovskite compound has the general formula (1): A"(B"+73B" 2/
3) Compounds represented by Ch, for example, Pb(TL/3Z
r2/3)03, Ba(Zn+z 3Nbt/3)0
3, Ba(Cd+z 3Nbtz y)C1+,Ba(
Mg+/3Nb2/ JO3,5r(Cd+/3Nbt
/3)03%P b(Mg+/3 N bt/3)'0
3, P b (N II73Nbt/3) 03, P b (
Mn+y zNbt/*)03, Pb(Mg+,z 3
Ta, /3) 03, Pb (Nl+7, Tat/a)
03, P b(Cd+73Nbt73)03; General formula (
II): A” (B””I/ 2B needle 1/2) 03
Compounds represented by, for example, Ba(F' eli tNb+/z)03, Ba(S,
c+/lNb+/2)03, Ca(Cr+/aNb+/
JO3, Pb(Pel/lNb+72)03, Pb(P
e+7 tTa+y t)03, Pb(Sc+/lNb
+/1) Os, Pb(Sc5z tTa+y t)03
, Pb(Yb+/lNb+/l)03, Pb(Yb+/l)
+/1TaI7 t)Os, Pb(Lu+/lNb+/
1) 03, Pb(Ir++/, Nb,, JO3; General formula (III): A""(B" I/ 2B"
Compounds represented by I/*)0+, for example, Pb(Cd+/lW1/ri03, Pb(Mr++/l
WI/Os, Pb(ZnI72Wl/JO3,
Pb(Mg+72Wl/t)O3゜Pb(Cot/
,wI/1)03,P b(N I 1/2W +/
2) 03,Pb(Mg+/1Te7t)03,P
b(Mn+/1Te72)03, P b(Co+/1T
el/1) Os, Pb(Cu+72W+/1)03 General formula (■): A” (B”” 273B” +/ 3
)0*, for example, Pb(Fet73V
b/*) Osni general formula (V): A” (B l/
t”B l/t”)03, for example, Pb(Sn+/lsb+/1)03, La(Mg+/
2T L7 t)03, Nd(Mg17tTL7 t
) Os; and general formula (VT): (A” I/ t
A3 “I/ 2) B” Compounds represented by 03, for example, CNa+y 2La+/JTiO*, (Kl/ , La
+/t)Tios, (Na+/lce+7t)Ti
O+, CNa, /zNd+/l)T io3, (Nd+
/2B i7 t)T io 3, (K +/ tB
L/t) TiO*, etc.
また、別に調整されたＢサイトまたはＡサイトの金属酸
化物とは、上記した工程を経て得られた複合酸化物でも
よく、あるいは市販の金属酸化物でもよい。Further, the separately prepared B site or A site metal oxide may be a composite oxide obtained through the above-described steps, or may be a commercially available metal oxide.
（作用）
本発明ハ、複合ペロブスカイト型化合物を構成する金属
元素をＡサイトとＢサイトの成分に分け、これらのＡサ
イトまたはＢサイトを湿式合成法により共沈体あるいは
沈澱物として析出させることによってミクロ的に均一に
混合、分散した原料粉末が得られるようにする一方、こ
れらの共沈体もしくは沈澱物を別々にロータリエバポレ
ータもしくはスプレードライヤーで乾燥させることによ
って溶出による損失を防止すると同時に、活性の高い粉
末を得、低温度での焼成を可能にし、これによって、所
望の組成を有する複合ペロブスカイト型化合物からなる
磁器が得られる。(Function) The present invention C. By dividing the metal element constituting the composite perovskite compound into A site and B site components, and precipitating these A site or B site as a coprecipitate or precipitate by a wet synthesis method. By drying these coprecipitates or precipitates separately using a rotary evaporator or a spray dryer, it is possible to obtain microscopically uniformly mixed and dispersed raw material powders, while preventing loss due to elution and at the same time reducing activity. A high powder is obtained, making it possible to fire at low temperatures, thereby obtaining a porcelain consisting of a composite perovskite type compound with the desired composition.
（実施例Ｉ）
硝酸マグネシウム（０，２４７２モル）、硝酸銅（０，
００７５５モル）、硝酸亜鉛（０，００２５１モル）、
硝酸チタニール（０，００３７７モル）、水酸化ニオブ
（０，５００モル）および酸化タングステン（０，００
７５５モル）を水に溶解もしくは分散させて混合スラリ
ーを調製し、これに３０％過酸化水素水とアンモニア水
の混合溶液を加えてｐｌ−（を９〜９．５に調整して沈
澱させる。生成した沈澱物を市販のロータリエバポレー
タを用いて脱溶媒を行い、得た乾燥粉末を空気中８００
℃で２時間仮焼して酸化物粉末を得た。(Example I) Magnesium nitrate (0,2472 mol), copper nitrate (0,
00755 mol), zinc nitrate (0,00251 mol),
Titanyl nitrate (0,00377 mol), niobium hydroxide (0,500 mol) and tungsten oxide (0,00 mol)
A mixed slurry is prepared by dissolving or dispersing 755 mol) in water, and a mixed solution of 30% hydrogen peroxide and ammonia water is added to adjust pl-( to 9 to 9.5 and precipitate. The resulting precipitate was desolvented using a commercially available rotary evaporator, and the resulting dry powder was heated in air for 800 min.
The mixture was calcined at ℃ for 2 hours to obtain an oxide powder.
次いで、これとは別に調製した、または市販の四三酸化
鉛（ｐｂ３ｏ、）を萌記酸化物粉末１００ｇに対して２
２１．５４１ｇ添加、混合し、仮焼して複合ペロブスカ
イト型化合物粉末を得、この粉末にバインダを加えて造
粒したのち、円板状圧粉体を成形し、１０００℃で２時
間焼成して０．９８５Ｐｂ（Ｍｇ＋／５Ｎｂｔ／３）０
３−０．０１０ Ｐｂ（Ｚｎ＋、ｚ ｔＷｌ／ ＪＯ３
−０，００５ＰｂＴｉ０３からなる主成分１００モル％
に２モル％のＰｂ（Ｃｕ＋７２Ｗ＋／ ２）０３を添加
した組成からなる誘電体磁器円板を得た。Next, separately prepared or commercially available trilead tetroxide (pb3o) was added at a rate of 2 to 100 g of Moeki oxide powder.
21.541g was added, mixed, and calcined to obtain a composite perovskite compound powder. After adding a binder to this powder and granulating it, a disc-shaped green compact was formed and fired at 1000°C for 2 hours. 0.985Pb(Mg+/5Nbt/3)0
3-0.010 Pb(Zn+,z tWl/ JO3
-100 mol% main component consisting of 0,005PbTi03
A dielectric ceramic disk was obtained having a composition in which 2 mol% of Pb(Cu+72W+/2)03 was added.
（実施例２）
硝酸ニッケル（０，２３４４モル）、硝酸ジルコニウム
（０，３５９４モル）、イソプロポキシチタン（０，５
０００モル）および水酸化ニオブ（０，４６５０モル）
を水に溶解して混合液を調製し、これに３０％過酸化水
素水とアンモニア水とを加えてｐＨを９〜９，５に調整
して沈澱を生成させる。(Example 2) Nickel nitrate (0,2344 mol), zirconium nitrate (0,3594 mol), isopropoxy titanium (0,5 mol)
000 mol) and niobium hydroxide (0,4650 mol)
is dissolved in water to prepare a mixed solution, and 30% hydrogen peroxide and aqueous ammonia are added thereto to adjust the pH to 9 to 9.5 to form a precipitate.
この沈澱物を実施例１と同様に、脱溶媒、仮焼して得た
酸化物粉末１００ｇに対してこれとは別に調整し、また
は市販の四三酸化鉛（ＰｂｓＯ４）２３４．０８１ｇを
添加して仮焼し、複合ペロブスカイト型化合物粉末を得
、これにバインダーを添加してペースト状にし、ドクタ
ーブレード法にてシート化し、これを１１００℃で２時
間焼成して、０ 、’４５ Ｐｂ（ＮＬ／３Ｎｂ、／３
）０３−０．３２ ＰｂＴｉＯ３−０，２３ＰｂＺｒＯ
ｓからなる圧電体磁器を得た。This precipitate was separately adjusted to 100 g of oxide powder obtained by removing the solvent and calcining in the same manner as in Example 1, or 234.081 g of commercially available trilead tetraoxide (PbsO4) was added. A composite perovskite compound powder was obtained, a binder was added to the powder, and a binder was added to form a paste, which was then formed into a sheet using a doctor blade method. This was then fired at 1100°C for 2 hours to obtain 0,'45 Pb (NL). /3Nb, /3
)03-0.32 PbTiO3-0,23PbZrO
A piezoelectric ceramic made of s was obtained.
（発明の効果）
以上の説明から明らかなように、本発明によれば、湿式
合成した共沈体を洗浄、脱水することなくロークリエバ
ポレータやスプレードライヤで溶媒のみを除去するため
、原料粉末製造時に磁器成分の溶出による損失を全く生
じることがない。しかも、複合ペロブスカイト型化合物
のＡサイトの成分とＢサイトの成分とを酸化物の形態で
別々に生成させ、その後に両成分を混合して複合ペロブ
スカイト化合物を生成させるため、特に、鉛を含む複合
ペロブスカイト化合物の場合でも、鉛をｐｂ３ｏ、の形
態で添加して焼成するため、従来のように鉛が蒸発する
ことはなく、従って、モル比にズレのない磁器を得ろこ
とができる。さらに、本発明方法では、Ａサイトおよび
Ｂサイトの成分でそれぞれ複合酸化物の結晶を初めに構
築させているため、焼成時にパイロクロアの生成が非常
に少なく、従って、比較的低い温度で焼成することがで
きろ、など優れた効果が得られる。(Effects of the Invention) As is clear from the above description, according to the present invention, since only the solvent is removed using a low evaporator or a spray dryer without washing or dehydrating the wet-synthesized coprecipitate, raw material powder production is possible. At times, there is no loss of porcelain components due to elution. Moreover, since the A-site component and the B-site component of the composite perovskite compound are generated separately in the form of oxides, and then both components are mixed to produce the composite perovskite compound, it is especially Even in the case of a perovskite compound, since lead is added in the form of PB3O and fired, the lead does not evaporate unlike in the past, and therefore it is possible to obtain porcelain with no deviation in molar ratio. Furthermore, in the method of the present invention, since composite oxide crystals are first constructed from the components of the A site and the B site, very little pyrochlore is produced during firing, and therefore, firing can be performed at a relatively low temperature. Excellent effects can be obtained, such as:
Claims (1)
’＿１＿−＿ｙ）Ｏ＿３（式中、ＡサイトのＡおよびＡ
’は同じ又は異なる１価または２価の金属、Ｂサイトの
ＢおよびＢ’は同じ又は異なる２〜６価の金属を表す。 ）で示される複合ペロブスカイト型化合物からなる複合
酸化物磁器の製造方法において、 前記複合ペロブスカイト型化合物のＡサイトまたはＢサ
イトの金属元素の硝酸塩および水酸化物からなる群から
選ばれた少なくとも二つの水溶性金属化合物を含む水溶
液に、アンモニア水を加えて共沈体を生成させ、該共沈
体をロータリエバポレイータもしくはスプレイドライヤ
ーで溶媒を除去したのち、得られた乾燥粉末を仮焼して
ＡサイトまたはＢサイトの金属元素の複合酸化物を生成
させ、該ＡサイトまたはＢサイトの金属元素の複合酸化
物を、それとは別に調製されたＢサイトまたはＡサイト
の金属酸化物と精秤、混合して焼成することを特徴とす
る複合酸化物磁器の製造方法。(1) General formula: (A_xA'_1_-_x) (B_yB
'_1_-_y)O_3 (where A and A at A site
' represents the same or different monovalent or divalent metal, and B and B' at the B site represent the same or different divalent to hexavalent metal. ), in which at least two water-soluble porcelains selected from the group consisting of nitrates and hydroxides of metal elements at the A site or B site of the composite perovskite compound are provided. Aqueous ammonia is added to an aqueous solution containing a metal compound to form a coprecipitate, the solvent is removed from the coprecipitate using a rotary evaporator or a spray dryer, and the resulting dry powder is calcined to produce A. A composite oxide of a metal element at the A site or B site is generated, and the composite oxide of the metal element at the A site or B site is accurately weighed and mixed with a separately prepared metal oxide at the B site or A site. A method for manufacturing composite oxide porcelain, which comprises firing the composite oxide porcelain.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63202892A JPH0251463A (en) | 1988-08-15 | 1988-08-15 | Preparation of multiple oxide ceramic |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63202892A JPH0251463A (en) | 1988-08-15 | 1988-08-15 | Preparation of multiple oxide ceramic |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0251463A true JPH0251463A (en) | 1990-02-21 |
Family
ID=16464929
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63202892A Pending JPH0251463A (en) | 1988-08-15 | 1988-08-15 | Preparation of multiple oxide ceramic |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0251463A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6153114A (en) * | 1984-08-18 | 1986-03-17 | Natl Inst For Res In Inorg Mater | Production of powdery raw material of easily sintering perovskite solid solution |
-
1988
- 1988-08-15 JP JP63202892A patent/JPH0251463A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6153114A (en) * | 1984-08-18 | 1986-03-17 | Natl Inst For Res In Inorg Mater | Production of powdery raw material of easily sintering perovskite solid solution |
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