JPH027906B2 - - Google Patents
Info
- Publication number
- JPH027906B2 JPH027906B2 JP60210771A JP21077185A JPH027906B2 JP H027906 B2 JPH027906 B2 JP H027906B2 JP 60210771 A JP60210771 A JP 60210771A JP 21077185 A JP21077185 A JP 21077185A JP H027906 B2 JPH027906 B2 JP H027906B2
- Authority
- JP
- Japan
- Prior art keywords
- powder
- perovskite
- zirconium
- ceramics
- density
- 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
Links
- 239000000843 powder Substances 0.000 claims description 48
- 239000000919 ceramic Substances 0.000 claims description 20
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 19
- 229910052726 zirconium Inorganic materials 0.000 claims description 16
- 238000001354 calcination Methods 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 230000001476 alcoholic effect Effects 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 17
- 239000002245 particle Substances 0.000 description 14
- 239000002994 raw material Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 9
- 239000010936 titanium Substances 0.000 description 6
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 5
- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- 229910052715 tantalum Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 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
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
Description
【発明の詳細な説明】
産業上の利用分野
本発明はジルコニウムを含むペロブスカイトセ
ラミツクスの製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a method for producing perovskite ceramics containing zirconium.
ペロブスカイトセラミツクスは圧電体、オプト
エレクトロニクス材料、誘電体、半導体、センサ
ーなどの機能性セラミツクスとして広範囲の分野
で利用されている。 Perovskite ceramics are used in a wide range of fields as functional ceramics such as piezoelectric materials, optoelectronic materials, dielectrics, semiconductors, and sensors.
従来技術
重要なペロブスカイト系機能性セラミツクスに
は、ジルコニウムを含むものが極めて多い。Prior Art A significant number of important perovskite-based functional ceramics contain zirconium.
これらの構成成分の原料粉末の中で、ジルコニ
ヤ原料粉末は極めて凝集し易い。この様なジルコ
ニヤ原料粉末を使用して乾式法でペロブスカイト
原料粉末を作成しても平均粒径は１〜2μm以上の
ものとなる。この程度の粒度のペロブスカイト原
料粉末を使用しても、高密度且つ高度な機能の機
能性セラミツクスを得ることは難しい。 Among the raw material powders of these constituent components, the zirconia raw material powder is extremely likely to aggregate. Even if a perovskite raw material powder is produced by a dry method using such a zirconia raw material powder, the average particle size will be 1 to 2 μm or more. Even if a perovskite raw material powder with a particle size of this size is used, it is difficult to obtain functional ceramics with high density and advanced functionality.
発明の目的
本発明は前記のジルコニウムを含むペロブスカ
イト系セラミツクスの乾式法による合成における
欠点を解消すべくなされたもので、その目的は、
分散性の良いサブミクロン級の変成ジルコニヤ原
料粉末を作成し、該粉末を用いて単なる乾式法に
よつて易焼結性且つ高嵩密度の各種ペロブスカイ
ト粉末を合成し、更にこれら粉末を焼結して高性
能且つ高密度のペロブスカイト系機能性セラミツ
クスを製造する方法を提供するにある。OBJECTS OF THE INVENTION The present invention was made to overcome the drawbacks in the dry synthesis of zirconium-containing perovskite ceramics, and its purpose is to:
A submicron-grade modified zirconia raw material powder with good dispersibility is created, and this powder is used to synthesize various easily sinterable and high bulk density perovskite powders by a simple dry method, and these powders are further sintered. An object of the present invention is to provide a method for producing high-performance, high-density perovskite-based functional ceramics.
発明の構成
本発明者らは前記目的を達成すべく鋭意研究の
結果、
一般式ABO3（ただし、Ａは酸素12配位金属元
素、Ｂは酸素６配位金属元素を示す）で示される
ジルコニウム（Ｂ位置）を含むペロブスカイトセ
ラミツクスの乾式法による製造過程において、ペ
ロブスカイト化合物を構成するジルコニウム以外
の少なくとも一成分の全量でない適量とジルコニ
ウムの全量を含む溶液との混合溶液（水溶液又は
アルコール溶液）を作り、該混合液と沈殿形成液
とを混合することなどにより共沈体を形成し、乾
燥後、700〜1300℃で仮焼すると、凝集の極めて
少ないサブミクロン級の粉末（変成ジルコニヤ粉
末）となし得ることが分つた。これを原料とし、
目的とするペロブスカイト組成の残りの構成部分
量の化合物を乾式法によつて混合すれば、サブミ
クロン級の粉末特性の優れた原料粉末が容易に得
られ、これを成型して焼結すると、焼結助剤なし
に極めて高密度のペロブスカイトセラミツクスが
容易に得られることを究明し得た。この知見に基
いて本発明を完成した。Structure of the Invention As a result of intensive research to achieve the above object, the present inventors found that zirconium represented by the general formula ABO 3 (where A is a 12-coordinated metal element of oxygen and B is a 6-coordinated metal element of oxygen) In the dry manufacturing process of perovskite ceramics containing (B position), a mixed solution (aqueous or alcoholic solution) is made of an appropriate amount but not the entire amount of at least one component other than zirconium constituting the perovskite compound and a solution containing the entire amount of zirconium. A coprecipitate is formed by mixing the mixed liquid and a precipitate forming liquid, and after drying, it is calcined at 700 to 1300°C to form a submicron-grade powder (modified zirconia powder) with extremely low agglomeration. I found out that I can get it. Using this as raw material,
By dry-mixing the remaining components of the desired perovskite composition, a raw material powder with excellent submicron powder properties can be easily obtained. We have found that extremely high density perovskite ceramics can be easily obtained without using binders. The present invention was completed based on this knowledge.
本発明の要旨は、
(1) ペロブスカイト化合物を構成するジルコニウ
ム以外の少なくとも一成分の全量でない適量
と、ジルコニウムの全量を含む溶液との混合溶
液（水溶液又はアルコール溶液）を作り、これ
と沈殿形成液とを混合することなどにより共沈
体を形成し、乾燥後700〜1300℃で仮焼する工
程、
(2) この仮焼物と、目的とするペロブスカイト組
成の残りの構成成分量の化合物を混合して500
〜1300℃で仮焼する工程
(3) 得られた仮焼粉末を成型して700〜1700℃で
焼結する工程とからなることを特徴とするジル
コニウムを含むペロブスカイトセラミツクスの
製造方法。 The gist of the present invention is to: (1) prepare a mixed solution (aqueous solution or alcohol solution) of an appropriate amount but not the entire amount of at least one component other than zirconium constituting a perovskite compound and a solution containing the entire amount of zirconium; (2) mixing this calcined product with a compound in the amount of the remaining components of the desired perovskite composition; 500
A method for producing perovskite ceramics containing zirconium, comprising the following steps: (3) calcination at a temperature of 1300°C to 1300°C; and sintering the resulting calcined powder at 700 to 1700°C.
にある。It is in.
前記一般式ABO3で示されるペロブスカイト化
合物のＡ成分（酸素12配位金属元素）としては、
例えばPb，Ba，Ca，Sr及びLaなどの希土類元
素が挙げられる。またＢ成分（酸素６配位金属元
素）としては、ジルコニウムのほか、例えば、
Ti，Mg，Sc，Hf，Th，Ｗ，Nb，Ta，Cr，
Mo，Mn，Fe，Co，Ni，Cd，Al，Sn，As，
Bi，等が挙げられる。 The A component (oxygen 12-coordinated metal element) of the perovskite compound represented by the general formula ABO 3 is as follows:
Examples include rare earth elements such as Pb, Ba, Ca, Sr, and La. In addition to zirconium, the B component (oxygen hexacoordination metal element) includes, for example,
Ti, Mg, Sc, Hf, Th, W, Nb, Ta, Cr,
Mo, Mn, Fe, Co, Ni, Cd, Al, Sn, As,
Examples include Bi, etc.
なお、本発明においては、これらのＡ成分とＢ
成分のモル比が1.0より高い値あるいは低い値に
ずらしたものも含む。 In addition, in the present invention, these A components and B
It also includes those in which the molar ratio of the components is shifted to a value higher or lower than 1.0.
また、ペロブスカイト系機能性セラミツクスに
おいては、その焼結性や特性を改善するために、
一般に微量の助剤を添加するのが通例であり、こ
れらの助剤は(1)，(2)の工程で適当に添加すればよ
い。 In addition, in order to improve the sinterability and properties of perovskite-based functional ceramics,
Generally, it is customary to add a small amount of auxiliary agents, and these auxiliary agents may be added appropriately in steps (1) and (2).
ジルコニウム溶液（水溶液又はアルコール溶
液）を作成するための化合物としては、オキシ塩
化ジルコニウム、オキシ硝酸ジルコニウム、塩化
ジルコニウム、硝酸ジルコニウム及び金属ジルコ
ニウムなどが挙げられる。 Examples of compounds for creating a zirconium solution (aqueous or alcoholic solution) include zirconium oxychloride, zirconium oxynitrate, zirconium chloride, zirconium nitrate, and metallic zirconium.
沈殿形成液作成のための試薬としては、例えば
アンモニヤ、炭酸アンモニウム、苛性アルカリ、
しゆう酸、しゆう酸アンモニウムやアミン類、オ
キシン、尿素、水酸化テトラメチルアンモン等の
有機試薬が挙げられる。 Examples of reagents for preparing a precipitate-forming solution include ammonia, ammonium carbonate, caustic alkali,
Examples include organic reagents such as oxalic acid, ammonium oxalate, amines, oxine, urea, and tetramethylammonium hydroxide.
ジルコニウム溶液に添加するペロブスカイトの
構成成分の種類とその量は、構成成分の添加によ
つて最終的に得られる変成ジルコニヤ粉末の凝集
を抑制し得られるものであることが必要である
が、また、ペロブスカイト機能セラミツクスに共
通して含まれる成分であることが好ましい。得ら
れた共沈体の仮焼温度は、700〜1300℃である。
700℃より低いと凝集が顕著に起り、1300℃を超
えると粒子が粗大化する傾向がある。このように
して得られたものに、ジルコニウム以外の構成成
分の不足分を加えて混合する。勿論、ジルコニヤ
に添加した変成成分の不足分も補充する必要があ
る。この場合、いずれの化合物粉末（主として酸
化物）の粒度はサブミクロン級のものが好まし
い。ただ、酸化鉛粉末は粗大粒径のものを使用し
ても、得られるペロブスカイト粉末の特性に悪い
影響を与えない。 The types and amounts of the perovskite components added to the zirconium solution must be such that they can suppress agglomeration of the modified zirconia powder that is finally obtained by adding the components; Preferably, it is a component commonly contained in perovskite functional ceramics. The calcination temperature of the obtained coprecipitate is 700 to 1300°C.
When the temperature is lower than 700°C, significant aggregation occurs, and when the temperature exceeds 1300°C, the particles tend to become coarse. To the thus obtained mixture, the remaining components other than zirconium are added and mixed. Of course, it is also necessary to replenish the deficiency in the metamorphic components added to zirconia. In this case, the particle size of any compound powder (mainly oxide) is preferably submicron. However, even if lead oxide powder with a coarse particle size is used, it will not have a negative effect on the properties of the obtained perovskite powder.
これら混合物の仮焼温度は、Pbを含む場合、
BaやSrを含む場合、またNbやTaを含む場合と
で、500〜1300℃の範囲で大幅に変化する。要は
固相反応がほゞまたは完全に完了する最低温度以
上で、顕著な粒子成長が生じない温度範囲内であ
ることが必要である。 The calcination temperature of these mixtures is, when Pb is included,
The temperature varies greatly in the range of 500 to 1300°C depending on whether it contains Ba or Sr or Nb or Ta. In short, it is necessary that the temperature be higher than the minimum temperature at which the solid phase reaction is substantially or completely completed, and within a temperature range that does not cause significant particle growth.
このようにして得られた粉末を成型して焼結す
る。焼結温度は前記の混合物の仮焼温度と同様に
その構成成分の種類によつて異なるが、一般的に
700〜1700℃の範囲である。700℃より低いとPb
を含むペロブスカイトでも焼結が不十分であり、
1700℃を超えるとNbやTaを含む場合でも粒子が
粗大化したり、あるいは構成成分の揮発が起る。 The powder thus obtained is shaped and sintered. The sintering temperature, like the calcination temperature of the mixture described above, varies depending on the type of its constituent components, but generally
It is in the range of 700-1700℃. Pb below 700℃
Even perovskites containing
If the temperature exceeds 1700°C, the particles will become coarse even if they contain Nb or Ta, or the constituent components will volatilize.
実施例 １
四塩化チタン水溶液（1.3317／mol濃度）
43.57c.c.とオキシ硝酸ジルコニウム水溶液（1.146
／mol濃度）150c.c.とを混合した。この混合水
溶液を撹拌している6N―アンモニヤ水１中に
徐々に添加して、Ti4+とZr4+の水酸化物共沈体を
得た。これを洗浄、乾燥した後1100℃で仮焼して
（Ti0.2・Zr0.8）O2粉末を作成した。Example 1 Titanium tetrachloride aqueous solution (1.3317/mol concentration)
43.57cc and zirconium oxynitrate aqueous solution (1.146
/mol concentration) 150 c.c. This mixed aqueous solution was gradually added to stirring 6N-ammonium water 1 to obtain a hydroxide coprecipitate of Ti 4+ and Zr 4+ . This was washed, dried, and then calcined at 1100°C to produce (Ti 0.2 .Zr 0.8 ) O 2 powder.
この粉末の平均粒径は0.32μmであつた。 The average particle size of this powder was 0.32 μm.
該粉末3.5779ｇと市販のTiO2微粉末1.4981ｇ、
PbO粉末（平均粒径15μm）11.16ｇとを、ボール
ミルで一昼夜混合した後、740℃で１時間仮焼し
てPb（Zr0.5・Ti0.5）O3粉末を得た。その平均粒径
は0.32μmであつた。該粉末を1t／cm2で成型した
タブレツトを、鉛蒸気、酸素ガス共存雰囲気下、
1220℃で１時間焼結した。得られたものの密度は
7.95に達し、これは理論密度に極めて近い値であ
る。 3.5779 g of said powder and 1.4981 g of commercially available TiO 2 fine powder,
11.16 g of PbO powder (average particle size 15 μm) was mixed in a ball mill overnight, and then calcined at 740° C. for 1 hour to obtain Pb(Zr 0.5 ·Ti 0.5 )O 3 powder. Its average particle size was 0.32 μm. A tablet made of 1 t/cm 2 of the powder was molded in an atmosphere coexisting with lead vapor and oxygen gas.
It was sintered at 1220°C for 1 hour. The density of the obtained product is
7.95, which is very close to the theoretical density.
比較例 １
市販のPbO，TiO2，ZrO2粉末をPb（Zr0.5・
Ti0.5）O3の組成になるように配合し、ボールミ
ルで１昼夜混合した後、850℃で２時間仮焼した。
この粉末を1t／cm2で成型し、実施例１と同じ条件
下で焼結した。Comparative Example 1 Commercially available PbO, TiO 2 , ZrO 2 powder was mixed with Pb (Zr 0.5 .
The mixture was blended to have a composition of Ti 0.5 ) O 3 , mixed in a ball mill for a day and night, and then calcined at 850° C. for 2 hours.
This powder was molded at 1 t/cm 2 and sintered under the same conditions as in Example 1.
得られたセラミツクスの密度は6.5程度であつ
た。なお、仮焼時での粉末の平均粒径は2.3μmで
あつた。 The density of the obtained ceramics was about 6.5. Note that the average particle size of the powder at the time of calcination was 2.3 μm.
実施例 ２
実施例１におけると同様にして作成した
（Ti0.2・Zr0.8）O2粉末2.8639ｇ、市販のTiO2微粒
子1.1985ｇ、PbO粉末11.16ｇ、Nb2O5微粒子
0.8861ｇ、水酸化コバルトを750℃で焼成して得
たCo3O4粉末0.2675ｇをボールミルで１昼夜混合
した後、750℃で１時間仮焼して0.2Pb（Co1/3・
Nb2/3）O3―0.4PbTiO3―0.4PbZrO3三成分系圧
電セラミツクス用粉末を得た。この平均粒径は約
0.39μmであつた。この粉末を1t／cm2で成型した
後、1200℃で１時間鉛蒸気、酸素ガス共存雰囲気
下で焼結した。Example 2 2.8639 g of (Ti 0.2 Zr 0.8 ) O 2 powder prepared in the same manner as in Example 1, 1.1985 g of commercially available TiO 2 fine particles, 11.16 g of PbO powder, Nb 2 O 5 fine particles
0.8861g and 0.2675g of Co 3 O 4 powder obtained by calcining cobalt hydroxide at 750℃ were mixed in a ball mill for one day and night, and then calcined at 750℃ for 1 hour to produce 0.2Pb (Co 1/3 .
A three - component powder for piezoelectric ceramics was obtained. This average particle size is approximately
It was 0.39 μm. This powder was molded at 1 t/cm 2 and then sintered at 1200° C. for 1 hour in an atmosphere coexisting with lead vapor and oxygen gas.
得られたセラミツクスの密度は7.93で、理論密
度に極めて近かつた。 The density of the obtained ceramics was 7.93, which was very close to the theoretical density.
比較例 ２
市販のPbO，Nb2O5，TiO2，ZrO2，CoO粉末
を、0.2Pb（Co1/3・Nb2/3）O3―0.4PbTiO3―
0.4PbZrO3の組成になるように混合した。この混
合物をボールミルで一昼夜混合した後、800℃で
２時間仮焼した。得られた粉末を1t／cm2で成型
し、鉛蒸気、酸素ガス共存雰囲気下、1200℃で１
時間焼結した。得られたセラミツクスの密度は
6.8程度であつた。Comparative Example 2 Commercially available PbO, Nb 2 O 5 , TiO 2 , ZrO 2 , CoO powder was mixed into 0.2Pb(Co 1/3・Nb 2/3 )O 3 ―0.4PbTiO 3 ―
They were mixed to have a composition of 0.4PbZrO 3 . This mixture was mixed in a ball mill all day and night, and then calcined at 800°C for 2 hours. The obtained powder was molded at 1 t/cm 2 and heated at 1200℃ in an atmosphere coexisting with lead vapor and oxygen gas.
Sintered for hours. The density of the obtained ceramics is
It was around 6.8.
なお、仮焼して得られた粉末は大きな凝集体か
らなり、平均粒径は特定できなかつた。 The powder obtained by calcining consisted of large aggregates, and the average particle size could not be determined.
発明の効果
本発明の方法によると、第一工程によりペロブ
スカイト化合物ジルコニウム以外の構成成分の一
種以上を含むジルコニヤ粉末（変成ジルコニヤ粉
末）は、凝集粒子の極めて少ないサブミクロン粒
子となし得、これを使用することによつて、以後
単なる乾式法によつて、容易にサブミクロン級の
ペロブスカイト原料粉末が得られ、更にこれを原
料として理論密度に極めて近い高密度のセラミツ
クスが得られる、優れた効果を奏し得られる。そ
のほか次のような効果も奏し得られる。Effects of the Invention According to the method of the present invention, the zirconia powder (modified zirconia powder) containing one or more constituents other than the perovskite compound zirconium can be made into submicron particles with extremely few agglomerated particles in the first step. By doing so, submicron-level perovskite raw material powder can be easily obtained by a simple dry method, and furthermore, high-density ceramics that are extremely close to the theoretical density can be obtained using this as a raw material, which is an excellent effect. can get. In addition, the following effects can also be achieved.
(1) 仮焼によつて得られる変成ジルコニヤ粉末が
十分分散されたものが得られるため、仮焼物の
粉砕工程を特に必要としないで、原料粉末とし
て供給し得られる。(1) Since the modified zirconia powder obtained by calcining is sufficiently dispersed, it can be supplied as a raw material powder without the need for a particular pulverization step of the calcined product.
(2) 該仮焼変成ジルコニヤ粉末から乾式法で得ら
れるペロブスカイト粉末も単分散状態で得ら
れ、従つて粉砕工程を除いても十分易焼結性且
つ高嵩密度の特性を有する。(2) Perovskite powder obtained from the calcined modified zirconia powder by a dry method is also obtained in a monodisperse state, and therefore has characteristics of sufficiently easy sinterability and high bulk density even without the pulverization step.
(3) 極めて高密度のものを要求されるペロブスカ
イト系機能性セラミツクスをホツトプレスや
HIP（熱間ガス圧焼結）などの操作を省略して
単なる固相焼結によつて、かつ焼結助剤を必ず
しも必要とせずして、理論密度に極めて近い高
密度のものが得られる。(3) Perovskite-based functional ceramics, which require extremely high density, can be produced by hot pressing or
A high-density product extremely close to the theoretical density can be obtained by simply solid-phase sintering without operations such as HIP (hot gas pressure sintering), and without necessarily requiring a sintering aid. .
(4) 優れた粉末特性を有する変成ジルコニヤ粉末
を大量生産しておけば、これから出発して数限
りないジルコニヤと変成成分を含むペロブスカ
イト原料粉末及び高性能ペロブスカイト系機能
性セラミツクスを単なる乾式法により極めて安
価に供給し得る。(4) If modified zirconia powder with excellent powder properties is mass-produced, it will be possible to start from now on by producing countless perovskite raw powders containing zirconia and modified components, as well as high-performance perovskite-based functional ceramics, using a simple dry process. Can be supplied at low cost.
Claims (1)
ニウム以外の少なくとも一成分の全量でない適
量と、ジルコニウムの全量を含む溶液との水溶
液またはアルコール溶液からなる混合液を作
り、これと沈殿形成液とを混合するなどにより
共沈体を形成し、乾燥後700〜1300℃で仮焼す
る工程、 (2) この仮焼物と目的とするペロブスカイト組成
の残りの構成成分量の化合物を混合して500〜
1300℃で仮焼する工程 (3) 得られた仮焼粉末を成型して700〜1700℃で
焼結する工程とからなることを特徴とするジル
コニウムを含むペロブスカイトセラミツクスの
製造方法。[Claims] 1 (1) A mixed solution consisting of an aqueous or alcoholic solution of an appropriate amount, but not the entire amount, of at least one component other than zirconium constituting the perovskite compound and a solution containing the entire amount of zirconium is prepared, and this is used to form a precipitate. A process of forming a coprecipitate by mixing with a perovskite liquid, and calcining it at 700 to 1300℃ after drying. 500～
A method for producing perovskite ceramics containing zirconium, comprising the steps of: (3) calcining at 1300°C; and molding the obtained calcined powder and sintering at 700 to 1700°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60210771A JPS62191465A (en) | 1985-09-24 | 1985-09-24 | Manufacture of perovskite ceramics containing zirconium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60210771A JPS62191465A (en) | 1985-09-24 | 1985-09-24 | Manufacture of perovskite ceramics containing zirconium |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62191465A JPS62191465A (en) | 1987-08-21 |
| JPH027906B2 true JPH027906B2 (en) | 1990-02-21 |
Family
ID=16594864
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60210771A Granted JPS62191465A (en) | 1985-09-24 | 1985-09-24 | Manufacture of perovskite ceramics containing zirconium |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62191465A (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4832893A (en) * | 1986-12-17 | 1989-05-23 | Nippondenso Co., Ltd. | Method for producing a PLZT compound |
| JP2598786B2 (en) * | 1986-12-17 | 1997-04-09 | 日本電装株式会社 | Method for producing perovskite-based functional ceramic |
| JPS63288963A (en) * | 1987-05-21 | 1988-11-25 | Nippon Denso Co Ltd | Production of (pb, ba) (zr, ti)o3 |
| JPS63288961A (en) * | 1987-05-21 | 1988-11-25 | Nippon Denso Co Ltd | Production of (pb, la) (hf, ti)o3 |
| JPS63288962A (en) * | 1987-05-21 | 1988-11-25 | Nippon Denso Co Ltd | Production of (pb, sr) (zr, ti)o3 |
| JPS63288960A (en) * | 1987-05-21 | 1988-11-25 | Nippon Denso Co Ltd | Production of (pb, bi) (zr, ti)o3 |
| JPS63288958A (en) * | 1987-05-21 | 1988-11-25 | Nippon Denso Co Ltd | Production of sr(ce, zr)o3 type ceramic |
-
1985
- 1985-09-24 JP JP60210771A patent/JPS62191465A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62191465A (en) | 1987-08-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPS63156057A (en) | Manufacture of high density perovskite ceramics | |
| JPS6214489B2 (en) | ||
| JP2598786B2 (en) | Method for producing perovskite-based functional ceramic | |
| JPH027906B2 (en) | ||
| JPH0159967B2 (en) | ||
| JPS63151672A (en) | Manufacture of lead zirconate titanate base piezoelectric ceramic | |
| JPS63151673A (en) | Manufacture of lead zirconate titanate base piezoelectric ceramic | |
| JPS6363511B2 (en) | ||
| JPH0818867B2 (en) | Method for producing perovskite ceramics containing zirconium | |
| JPH0159205B2 (en) | ||
| JP2616772B2 (en) | Method for producing proton conductive ceramics | |
| JPH01172256A (en) | Raw power for producing easy-to-sinter lead | |
| JPS6259529A (en) | Production of powdery raw material of easily sinterable titanium-containing perovskite and solid solution thereof | |
| JPH0784345B2 (en) | Manufacturing method of perovskite ceramics | |
| JPS63288960A (en) | Production of (pb, bi) (zr, ti)o3 | |
| JP2533305B2 (en) | Manufacturing method of dielectric resonator material | |
| JPS6265907A (en) | Production of easy-to-sinter perovskite powder | |
| JPH0784350B2 (en) | Manufacturing method of perovskite ceramics | |
| JPS63285150A (en) | Production of neodymium-containing dielectric material ceramic | |
| JPS6259505A (en) | Production of easily sintered perovskite powder | |
| JPS63248704A (en) | Production of powder as starting material for multicomponent ceramic | |
| JPH0678188B2 (en) | Method for producing lead zirconate | |
| JPH0678187B2 (en) | Method for producing lead zirconate | |
| JPS63152813A (en) | Manufacture of ferrodielectric ceramic composition | |
| JPS63288957A (en) | Production of zirconia ceramic |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |