JPH01224210A - Production of perovskite oxide powder - Google Patents
Production of perovskite oxide powderInfo
- Publication number
- JPH01224210A JPH01224210A JP5065688A JP5065688A JPH01224210A JP H01224210 A JPH01224210 A JP H01224210A JP 5065688 A JP5065688 A JP 5065688A JP 5065688 A JP5065688 A JP 5065688A JP H01224210 A JPH01224210 A JP H01224210A
- Authority
- JP
- Japan
- Prior art keywords
- elements
- metallic
- aqueous solution
- polycation
- precipitate
- 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
- 239000000843 powder Substances 0.000 title claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 32
- 239000007864 aqueous solution Substances 0.000 claims abstract description 22
- 239000002244 precipitate Substances 0.000 claims abstract description 22
- 239000000470 constituent Substances 0.000 claims abstract description 8
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 8
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 7
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 7
- 229910052742 iron Inorganic materials 0.000 claims abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 4
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 37
- 150000002736 metal compounds Chemical class 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 16
- 238000010304 firing Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 7
- 239000003795 chemical substances by application Substances 0.000 abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 abstract description 7
- 239000001301 oxygen Substances 0.000 abstract description 7
- 238000001354 calcination Methods 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 6
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052776 Thorium Inorganic materials 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract description 3
- 229910052785 arsenic Inorganic materials 0.000 abstract description 3
- 229910052797 bismuth Inorganic materials 0.000 abstract description 3
- 229910052793 cadmium Inorganic materials 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 229910052802 copper Inorganic materials 0.000 abstract description 3
- 229910052735 hafnium Inorganic materials 0.000 abstract description 3
- 229910052748 manganese Inorganic materials 0.000 abstract description 3
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 3
- 229910052758 niobium Inorganic materials 0.000 abstract description 3
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 3
- 229910052721 tungsten Inorganic materials 0.000 abstract description 3
- 229910052725 zinc Inorganic materials 0.000 abstract description 3
- 229910052749 magnesium Inorganic materials 0.000 abstract description 2
- 150000007524 organic acids Chemical class 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 229910052706 scandium Inorganic materials 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 229910052715 tantalum Inorganic materials 0.000 abstract description 2
- 229910052718 tin Inorganic materials 0.000 abstract description 2
- 229910000765 intermetallic Inorganic materials 0.000 abstract 2
- 239000000243 solution Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 150000004703 alkoxides Chemical class 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000010936 titanium Substances 0.000 description 8
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 7
- 239000001099 ammonium carbonate Substances 0.000 description 7
- -1 organic acid salts Chemical class 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 235000012501 ammonium carbonate Nutrition 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- 229910001928 zirconium oxide Inorganic materials 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 229910052746 lanthanum Inorganic materials 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-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
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 239000012736 aqueous medium Substances 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000003989 dielectric material Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 150000002823 nitrates Chemical class 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 230000005693 optoelectronics Effects 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000011736 potassium bicarbonate Substances 0.000 description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 2
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 2
- 235000011118 potassium hydroxide Nutrition 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 101100481408 Danio rerio tie2 gene Proteins 0.000 description 1
- 101100481410 Mus musculus Tek gene Proteins 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 229910052789 astatine Inorganic materials 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 1
- 230000015654 memory Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical group 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/14—Methods for preparing oxides or hydroxides in general
- C01B13/36—Methods for preparing oxides or hydroxides in general by precipitation reactions in aqueous solutions
- C01B13/363—Mixtures of oxides or hydroxides by precipitation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Oxygen, Ozone, And Oxides In General (AREA)
- Compounds Of Iron (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明はペロブスカイト酸化物粉末の製造方法の改良に
関するものである。さらに詳しくいえば、本発明は圧電
体、誘電体、半導体、センサ、オプトエレクトロニクス
材などの機能性セラミックスの原料として好適に用いら
れる、易焼結性、均一性、高嵩密度および低コストなど
の優れた特徴を有するペロブスカイト酸化物粉末を効率
よく製造する方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to an improvement in a method for producing perovskite oxide powder. More specifically, the present invention is suitable for use as a raw material for functional ceramics such as piezoelectric materials, dielectric materials, semiconductors, sensors, and optoelectronic materials, and has properties such as easy sinterability, uniformity, high bulk density, and low cost. The present invention relates to a method for efficiently producing perovskite oxide powder having excellent characteristics.
［従来の技術］
ペロブスカイト酸化物は、一般式ＡＢＯｓ（ただし、Ａ
は酸素１２配位金属元素、Ｂは酸素６配位金属元素であ
る）で示されるペロブスカイト構造をもつ化合物であっ
て、誘電性や圧電性を有する上に、透明焼結体は電気−
光効果の特性を有することが知られており、これらの特
性を利用して、フィルター、超音波振動子、共振子など
の圧電体や誘電体、光シヤツター、光メモリーなどのオ
プトエレクトロニクス材、さらには半導体やセンサなど
の機能性セラミックスとして、幅広く用いられている。[Prior Art] Perovskite oxides have the general formula ABOs (however, A
is a 12-coordinated metal element of oxygen, and B is a 6-coordinated metal element of oxygen.
It is known to have optical effect properties, and these properties can be used to create piezoelectric and dielectric materials such as filters, ultrasonic vibrators, and resonators, as well as optoelectronic materials such as optical shutters and optical memories. are widely used as functional ceramics such as semiconductors and sensors.
最近では、このような機能性セラミックスを用いた部品
の小型化や用途の多様化が進んでおり、そのため、品質
に優れ、かつ易焼結性で低コストの原料粉末が要望され
ている。Recently, components using such functional ceramics have become smaller and their applications have become more diverse, and therefore there is a demand for raw material powders that are excellent in quality, easy to sinter, and low in cost.
従来、ペロブスカイト酸化物粉末の製造方法としては、
乾式法と湿式法とが知られている。前者の乾式法は、構
成成分の原料化合物（主として酸化物）をボールミルな
どを用いて混合したのち、高温で焼成する方法である。Conventionally, the method for manufacturing perovskite oxide powder is as follows:
Dry methods and wet methods are known. The former dry method is a method in which constituent raw material compounds (mainly oxides) are mixed using a ball mill or the like, and then fired at a high temperature.
しかしながら、この方法においては、均一組成のペロブ
スカイト酸化物粉末が得にくい上に、原料化合物を高温
で焼成するために、得られる粉末の粗大化を免れず、十
分な焼結性が得られないなどの欠点がある。However, with this method, it is difficult to obtain perovskite oxide powder with a uniform composition, and since the raw material compound is fired at a high temperature, the resulting powder inevitably becomes coarse, and sufficient sinterability cannot be obtained. There are drawbacks.
一方、湿式法としてはアルコキシド法、共沈法、などが
知られている。該アルコキシド法は、構成成分である各
種金属のアルコキシドを混合したのち、これに水を加え
て加水分解し、次いで加水分解物を焼成する方法である
（特開昭５７−８２１２０号公報）。しかしながら、こ
の方法においては、原料アルコキシドが極めて高価であ
るので、製造コストの上昇を免れない上、操作に危険性
を伴い、かつ焼結による寸法収縮が大きいなどの問題が
ある。On the other hand, known wet methods include an alkoxide method and a coprecipitation method. The alkoxide method is a method in which alkoxides of various metals as constituent components are mixed, water is added thereto for hydrolysis, and the hydrolyzate is then calcined (Japanese Unexamined Patent Publication No. 57-82120). However, in this method, since the raw material alkoxide is extremely expensive, there are problems such as an increase in manufacturing costs, a dangerous operation, and large dimensional shrinkage due to sintering.
また、共沈法は、その構成成分をすべて含む混合溶液を
調製し、これに沈殿形成剤を添加して、共沈物を得、次
いでこの共沈物を乾燥、焼成する方法である（特公昭４
４−８１０６号公報）。この方法は、操作が簡単で製造
コストが低いという長所を有するものの、各成分の沈殿
形成能が一定でないため、所望の組成のものが得られに
くい上、沈殿生成時や乾燥時、あるいは焼成時に粒子が
凝結して二次粒子を形成し、易焼結性になりにくい、な
どの欠点を有している。In addition, the coprecipitation method is a method in which a mixed solution containing all the constituent components is prepared, a precipitate is added to this to obtain a coprecipitate, and this coprecipitate is then dried and fired (specially Kosho 4
4-8106). Although this method has the advantage of easy operation and low manufacturing cost, it is difficult to obtain the desired composition because the precipitate forming ability of each component is not constant. It has drawbacks such as the particles coagulate to form secondary particles and are difficult to sinter.
他方、ペロブスカイト酸化物の構成元素の中で、Ｔｉ、
Ｚｒ、Ｃｒ、Ｆｅ、ＡｌおよびＧａは、水溶液中でポリ
カチオンを形成し、高いｐＨ領域でも均一なりリアゾル
を与えることが知られている［「近畿大学理工学研究報
告」第２０巻、第１３３ページ（１９８５年）］。On the other hand, among the constituent elements of perovskite oxide, Ti,
It is known that Zr, Cr, Fe, Al, and Ga form polycations in aqueous solution and provide a homogeneous lyasol even in a high pH region [Kinki University Science and Engineering Research Report, Vol. 20, No. 133] Page (1985)].
［発明が解決しようとする課題］
本発明は、従来のペロブスカイト酸化物粉末の製造方法
が有する欠点を克服し、易焼結性であり、かつ微細で均
一性に優れた高嵩密度のペロブスカイト酸化物粉末を、
低コストで効率よく製造する方法を提供することを目的
としてなされたものである。[Problems to be Solved by the Invention] The present invention overcomes the drawbacks of conventional methods for producing perovskite oxide powder, and produces a perovskite oxide powder that is easily sinterable, fine and highly uniform, and has a high bulk density. powder,
This was done with the aim of providing an efficient manufacturing method at low cost.
［課題を解決するための手段］
本発明者らは、前記目的を達成するために、操作が簡単
で製造コストの低い共沈法によるペロブスカイト酸化物
粉末の製造方法について鋭意研究を重ねた結果、前記金
属元素のポリカチオンクリアゾルと、他の金属元素を含
む可溶性金属化合物を含有する溶液とを沈殿形成剤の存
在下に接触させることにより、各成分の沈殿形成能の違
いを小さくすることができて、所望組成の沈殿を形成さ
せることができ、しかもこの沈殿を焼成してなるペロブ
スカイト酸化物粉末は、粒子径がサブミクロンオーダの
均一性に優れた高嵩密度の微粉末であり、かつ良好な焼
結性を有することを見い出し、この知見に基づいて本発
明を完成するに至った。[Means for Solving the Problems] In order to achieve the above object, the present inventors have conducted intensive research on a method for producing perovskite oxide powder using a coprecipitation method that is easy to operate and has low production costs. By bringing the polycation clear sol of the metal element into contact with a solution containing a soluble metal compound containing another metal element in the presence of a precipitate forming agent, it is possible to reduce the difference in the precipitate forming ability of each component. The perovskite oxide powder obtained by sintering this precipitate is a fine powder with a high bulk density and excellent uniformity with a particle size on the submicron order. It was discovered that it has good sinterability, and based on this knowledge, the present invention was completed.
すなわち、本発明は、構成金属元素として、Ｔｉ、Ｚｒ
−Ｃｒ、Ｆｅ、Ａｔ’およびＧａの中から選ばれた少な
くとも１種を含有するペロブスカイト酸化物粉末を湿式
法で製造するに当り、前記金属元素の中から選ばれた少
なくとも１種の金属元素のポリカチオンクリアゾルと、
前記以外の金属元素を含む可溶性金属化合物の水性溶液
とを、沈殿形成剤の存在下に接触させて沈殿を形成させ
、次いで該沈殿を焼成することを特徴とするペロブスカ
イト酸化物粉末の製造方法を提供するものである。That is, the present invention uses Ti, Zr as constituent metal elements.
- In producing perovskite oxide powder containing at least one selected from Cr, Fe, At' and Ga by a wet method, at least one metal element selected from the above metal elements is used. Polycation clear sol and
A method for producing perovskite oxide powder, which comprises contacting an aqueous solution of a soluble metal compound containing a metal element other than the above in the presence of a precipitant to form a precipitate, and then firing the precipitate. This is what we provide.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明方法で得られるペロブスカイト酸化物粉末は、一
般式、
ＡＢＯ，・・・（１）
（式中のＡは酸素１２配位金属元素、Ｂは酸素６配位金
属元素である）
で示されるペロブスカイト構造を有する金属酸化物の粉
末である。The perovskite oxide powder obtained by the method of the present invention is represented by the general formula: ABO, (1) (in the formula, A is a metal element with 12 coordinations of oxygen and B is a metal element with 6 coordinations of oxygen). It is a metal oxide powder with a perovskite structure.
前記一般式（１）におけるＡ成分の酸素１２配位金属元
素としては、たとえばｐｂや、Ｂａ、Ｃａ、Ｓｒなどの
アルカリ土類金属、Ｙ、Ｌａなとの希土類元素などが挙
げられる。該Ａ成分としては、これらの金属元素を１種
類含有していてもよいし、２種以上含有していてもよい
。また、Ｂ成分の酸素６配位金属元素としては、たとえ
ばＴｉ、Ｚｒ、Ｍｇ、Ｓｃ、Ｈｆ、Ｔｈ、Ｗ、Ｎｂ、Ｔ
ａ、Ｃｒ、Ｍｏ、’ Ｃｕ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、
Ｚｎ、Ｃｄ、Ａ１．Ｓｎ、Ａｓ、Ｂｉなどが挙げられる
。該Ｂ成分としては、これらの金属元素を１種含有して
いてもよいし、２種以上含有していてもよい。Examples of the oxygen-12-coordinated metal element of the component A in the general formula (1) include PB, alkaline earth metals such as Ba, Ca, and Sr, and rare earth elements such as Y and La. The A component may contain one type of these metal elements, or may contain two or more types of these metal elements. Further, as the oxygen hexacoordination metal element of the B component, for example, Ti, Zr, Mg, Sc, Hf, Th, W, Nb, T
a, Cr, Mo,' Cu, Mn, Fe, Co, Ni,
Zn, Cd, A1. Examples include Sn, As, Bi, and the like. The B component may contain one type of these metal elements, or may contain two or more types of these metal elements.
該ペロブスカイト酸化物における前記Ｂ成分の２種以上
の元素の組合わせは、Ｔ ｉ ”とＺｒ”との組合わせ
のように等原子価のものの組自わせで、任意にその割合
を変えうるちの（Ａ成分の場合も同様である）、またＢ
位置合体で電気的中性条件を満足するような、たとえば
１／２Ｆｅ”と１／２ ＮｂＳ”、２／３Ｆｅ”と１
／３ Ｗ″゛、１／２Ｍｇ２°と２／３ Ｎｂ”の組
合せのようなものでもよく、さらにＡ成分−の位！また
はＢ成分の位置において、過剰もしくは不足の電荷を有
し、これらの電荷を陽イオン欠陥、陰イオン欠陥の生成
によって補償するような、たとえばＢ成分のＴｉ”＋Ｗ
”の組合せく陽イオン欠陥補償）、Ｔ ｉ ”とＡ１３
°（陰イオン欠陥補償）、Ａ成分Ｌａ”とＢａ”との組
合せく陽イオン欠陥補償）などであってもよい、また、
本発明で得られるペロブスカイト酸化物は、Ａ成分とＢ
成分のモル比を１．０より高い値もしくは低い値にずら
してＢ位置またはＡ位置に空孔を導入した不定比性のも
のも含有する。The combination of two or more elements of the B component in the perovskite oxide is a combination of elements with equal valences, such as the combination of T i '' and Zr'', and the proportions can be arbitrarily changed. (The same applies to the case of A component), and B
For example, 1/2Fe'' and 1/2NbS'', 2/3Fe'' and 1
/3 W″゛, a combination of 1/2 Mg2° and 2/3 Nb” may also be used, and the A component -! Or, for example, Ti''+W of the B component has an excess or insufficient charge at the position of the B component, and these charges are compensated by the generation of cation defects and anion defects.
``Cation defect compensation), T i '' and A13
° (anion defect compensation), combination of A components La" and Ba" (cation defect compensation), etc.
The perovskite oxide obtained in the present invention consists of component A and component B.
It also includes non-stoichiometric ones in which holes are introduced at the B position or A position by shifting the molar ratio of the components to a value higher or lower than 1.0.
本発明方法においては、まず、ペロブスカイト酸化物を
構成する元素の中から、ポリカチオンクリアゾルを形成
しうる元素を選び、そのポリカチオンクリアゾルを形成
させる。このような元素としては、Ｔｉ、Ｚｒ、Ｃｒ、
Ｆｅ、Ａ１およびＧａが挙げられる。ポリカチオンクリ
アゾルの形成方法については、前記金属元素を含む可溶
性金属化合物の１種または２種以上を水性媒体に溶解さ
せ、この溶液にアルカリを添加し、熟成させることによ
り、ポリカチオンクリアゾルを形成させることができる
。該可溶性金属化合物としては、たとえば硝酸塩、塩化
物、アルコキシド、有機酸塩などを挙げることができる
が、焼成過程において容易に分解し、陰イオン基が残留
しにくいもの、たとえば硝酸塩やアルコキシドが好適で
ある。In the method of the present invention, first, an element capable of forming a polycation clear sol is selected from among the elements constituting the perovskite oxide, and the polycation clear sol is formed. Such elements include Ti, Zr, Cr,
Mention may be made of Fe, A1 and Ga. Regarding the method for forming a polycation clear sol, one or more of the soluble metal compounds containing the above metal elements are dissolved in an aqueous medium, an alkali is added to this solution, and the solution is aged to form a polycation clear sol. can be formed. Examples of the soluble metal compound include nitrates, chlorides, alkoxides, organic acid salts, etc., but those that easily decompose during the firing process and do not easily leave anionic groups, such as nitrates and alkoxides, are preferred. be.
この金属化合物の濃度は、通常０．０１〜ｌＯモル／ｉ
の範囲で選ばれる。この濃度が低すぎると生産性が低く
て実用的でないし、高すぎると凝集体が生成するおそれ
があり、好ましくない、また、添加するアルカリとして
は、たとえば、アンモニア、水酸化ナトリウム、水酸化
カリウム、炭酸ナトリウム、炭酸カリウム、炭酸アンモ
ニウム、炭酸水素カリウム、炭酸水素ナトリウム、炭酸
水素アンモニウムなどが挙げられるが、これらの中で特
に炭酸塩が好ましい、これらのアルカリは、水性溶液と
して添加することが望ましい。The concentration of this metal compound is usually 0.01 to 10 mol/i
selected within the range. If this concentration is too low, productivity will be low and impractical; if it is too high, aggregates may form, which is undesirable.Additionally, the alkalis to be added include, for example, ammonia, sodium hydroxide, and potassium hydroxide. , sodium carbonate, potassium carbonate, ammonium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, ammonium hydrogen carbonate, etc. Among these, carbonates are particularly preferred.These alkalis are preferably added as an aqueous solution. .
ポリカチオンクリアゾルの形成は、通常Ｏ℃ないし沸点
の範囲の温度において行われ、熟成時間は通常１００時
間以内で十分である。このようにして、ポリカチオンク
リアゾルが形成されるが、ここでいうクリアゾルとは、
該可溶性金属化合物の加水分解によって生成した含水酸
化物のゾルであって、その中に沈殿物を含まないものの
ことである。The formation of the polycationic clear sol is usually carried out at a temperature ranging from 0° C. to the boiling point, and a maturing time of 100 hours or less is usually sufficient. In this way, a polycation clear sol is formed, but the clear sol here is
A sol of a hydrous oxide produced by hydrolysis of the soluble metal compound, which does not contain any precipitate.
一方、ペロブスカイト酸化物の構成成分ＡおよびＢの元
素の中から、前記金属化合物の金属元素以外の金属元素
を選び、この金属元素を含む可溶性金属化合物の１種ま
たは２種以上を水性媒体中に溶かして水性溶液を調製す
る。この可溶性金属化合物としては、たとえばＢａ、Ｃ
ａ、Ｓｒなどのアルカリ土類金属、Ｙ、Ｌａなとの希土
類元素、ＰｂＳＭｇ５Ｓｃ、Ｈｆ、Ｔｈ、Ｗ、Ｎｂ。On the other hand, a metal element other than the metal element of the metal compound is selected from among the elements of constituent components A and B of the perovskite oxide, and one or more soluble metal compounds containing this metal element are added to an aqueous medium. Dissolve to prepare an aqueous solution. Examples of this soluble metal compound include Ba, C
a, alkaline earth metals such as Sr, rare earth elements such as Y, La, PbSMg5Sc, Hf, Th, W, Nb.
Ｔａ、Ｍｏ、Ｃｕ、Ｍｎ、Ｃｏ、Ｎｉ、Ｚｎ、Ｃｄ、Ｓ
ｎ、Ａｓ、Ｂｉなどの硝酸塩、塩化物、アルコキシド、
有機酸塩などが挙げられるが、焼成過程において容易に
分解し、陰イオン基が残留しにくいもの、たとえば硝酸
塩やアルコキシドが好適である。これらの可溶性金属化
合物の濃度は、通常０．０１〜１０モル／１の範囲で選
ばれる。この濃度が低すぎると生産性が低くて実用的で
ないし、高すぎると凝集体が生成するおそれがあり、好
ましくない。Ta, Mo, Cu, Mn, Co, Ni, Zn, Cd, S
Nitrate, chloride, alkoxide, such as n, As, Bi, etc.
Examples include organic acid salts, but those that are easily decomposed during the firing process and do not easily leave anionic groups, such as nitrates and alkoxides, are preferred. The concentration of these soluble metal compounds is usually selected within the range of 0.01 to 10 mol/1. If this concentration is too low, productivity will be low and it is not practical, and if this concentration is too high, aggregates may be formed, which is not preferable.
本発明においては、この可溶性金属化合物を含有する水
性溶液と前記のポリカチオンクリアゾルとを、沈殿形成
剤の存在下に接触させて沈殿を形成させる。該沈殿形成
剤としては、たとえばアンモニア、水酸化ナトリウム、
水酸化カリウム、炭酸アンモニウム、炭酸水素ナトリウ
ム、炭酸水素カリウム、炭酸水素アンモニウムなどのア
ルカリや、シュウ酸、クエン酸などの有機酸、あるいは
メチルアミン、ジメチルアミン、トリメチルアミン、エ
チルアミン、ジエチルアミン、トリエチルアミン、プロ
ピルアミン、ジプロピルアミンなどのモノ、ジ、トリ低
級アルキルアミンなどが挙げられる。In the present invention, a precipitate is formed by bringing the aqueous solution containing the soluble metal compound into contact with the polycation clear sol in the presence of a precipitant. Examples of the precipitating agent include ammonia, sodium hydroxide,
Alkali such as potassium hydroxide, ammonium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, ammonium hydrogen carbonate, organic acids such as oxalic acid, citric acid, or methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine. and mono-, di-, and tri-lower alkyl amines such as dipropylamine.
本発明方法においては、沈殿形成剤の存在下に該ポリカ
チオンクリアゾルと、該可溶性金属化合物の水性溶液と
を接触させる方法ついては特に制限はなく、たとえば（
１）沈殿形成剤と可溶性金属化合物とを含有する水性溶
液中に、ポリカチオンクリアゾルを加えて混合する方法
、（２）沈殿形成剤を含む水性溶液中に、ポリカチオン
クリアゾルと可溶性金属化合物の水性溶液とを添加し、
混合する方法、（３）ポリカチオンクリアゾルと可溶性
金属化合物の水性溶液とを混合し、これに沈殿形成剤を
添加する方法、あるいは（４）沈殿形成剤を含有するポ
リカチオンクリアゾル中に、可溶性金属化合物の水性溶
液を添加し、混合する方法など、任意の方法を用いるこ
とができるが、これらの方法の中で、（２）の方法が好
適である。In the method of the present invention, there is no particular restriction on the method of bringing the polycation clear sol into contact with the aqueous solution of the soluble metal compound in the presence of a precipitant.
1) A method of adding and mixing a polycation clear sol into an aqueous solution containing a precipitation forming agent and a soluble metal compound, (2) A method of adding a polycation clear sol and a soluble metal compound to an aqueous solution containing a precipitation forming agent. and an aqueous solution of
(3) a method of mixing a polycation clear sol and an aqueous solution of a soluble metal compound and adding a precipitate forming agent thereto; Any method can be used, such as adding and mixing an aqueous solution of a soluble metal compound, but among these methods, method (2) is preferred.
この（２）の方法においては、沈殿形成剤を含有する水
性溶液中に、可溶性金属化合物の水性溶液とポリカチオ
ンクリアゾルとを同時に添加し、混合することが望まし
い、これらの方法においては、いずれも液を激しく撹拌
しながら行うことが好ましい、沈殿の形成は、通常０℃
ないし沸点の範囲の温度において行われ、また熟成時間
は、通常１００時間以内で十分である。In this method (2), it is desirable to simultaneously add and mix the aqueous solution of the soluble metal compound and the polycation clear sol into the aqueous solution containing the precipitant. Precipitate formation is preferably carried out while stirring the liquid vigorously, usually at 0°C.
The aging process is carried out at a temperature in the range of from to boiling point, and the aging time is usually 100 hours or less.
本発明方法において、前記各種溶液の調製に用いられる
水性媒体としては、水や、メタノール、エタノール、ア
セント、ジエチルエーテルなどの水と相溶性のある有機
溶媒、あるいは水とこれらの有機溶媒との混合溶媒など
を挙げることができる。In the method of the present invention, the aqueous medium used to prepare the various solutions mentioned above includes water, organic solvents that are compatible with water such as methanol, ethanol, ascent, and diethyl ether, or mixtures of water and these organic solvents. Examples include solvents.
次に、このようにして形成された沈殿は、付着する陽イ
オンや陰イオンなどを除去するために、水や、エタノー
ル、イソプロパツールなどのアルコールなどを用いて十
分に洗浄したのち、ろ別し、乾燥後、焼成する。乾燥は
、通常３０〜２００℃の範囲の温度において、１〜１０
０時間行われ、焼成は、好ましくは酸化性雲囲気下、た
とえば空気中において、通常４００〜１０００℃の範囲
の温度において、０．５〜１００時間程度行われる。Next, the precipitate formed in this way is thoroughly washed with water, alcohol such as ethanol, isopropanol, etc. to remove attached cations and anions, and then filtered. After drying, it is fired. Drying is usually carried out at a temperature in the range of 30 to 200°C for 1 to 10 minutes.
The calcination is preferably carried out under an oxidizing cloud atmosphere, for example in air, at a temperature usually in the range of 400 to 1000° C. for about 0.5 to 100 hours.
焼成温度が低すぎたり、焼成時間が短すぎたりすると固
相反応が進行しないことがあるし、焼成温度が高すぎた
り、焼成時間が長すぎたりすると粒子の焼結が進行し、
粒子の粗大化が起きるおそれがある。If the calcination temperature is too low or the calcination time is too short, the solid phase reaction may not proceed; if the calcination temperature is too high or the calcination time is too long, the particles will sinter.
There is a risk that particles will become coarser.
なお、本発明においては、ペロブスカイトの焼結性や特
性を制御するために、所望に応じ、微量成分を添加する
ことができる。この微量成分の添加については、構成成
分の水性溶液を調製する際に添加してもよいし、また、
ペロブスカイト酸化物粉末生成後、これに、乾式もしく
は湿式的に添加してもよい。In the present invention, trace components can be added as desired in order to control the sinterability and properties of the perovskite. Regarding the addition of this trace component, it may be added when preparing the aqueous solution of the component, or
After the perovskite oxide powder is produced, it may be added to the powder in a dry or wet manner.
［発明の効果］
本発明方法によると、ペロブスカイト酸化物を構成する
金属元素の中でポリカチオンクリアゾル￥
を形成しうる元素を選び、まずｌのポリカチオンクリア
ゾルを形成させ、このクリアゾルと、他の金属元素を含
む可溶性金属化合物の水性溶液とを、沈殿形成剤の存在
下に接触させることにより、従来の沈殿法の欠点である
各成分の沈殿形成能の違いを小さくすることができて、
所望組成の沈殿を形成させることができ、このようにし
て得られた沈殿を焼成することによって、粒子径がサブ
ミクロンオーダの均一性に優れた高嵩密度の易焼結性へ
ロブスカイト粉末を容易にかつ低コストで得ることがで
きる。[Effects of the Invention] According to the method of the present invention, an element capable of forming a polycation clear sol is selected from among the metal elements constituting the perovskite oxide, first, a polycation clear sol of l is formed, and this clear sol and By contacting an aqueous solution of a soluble metal compound containing other metal elements in the presence of a precipitate-forming agent, it is possible to reduce the difference in the precipitate-forming ability of each component, which is a drawback of conventional precipitation methods. ,
It is possible to form a precipitate with a desired composition, and by firing the precipitate thus obtained, it is possible to easily obtain a high bulk density, easily sinterable lobskite powder with excellent uniformity of particle size on the submicron order. can be obtained at low cost.
本発明方法で得られたペロブスカイト酸化物粉末は前記
したように優れた特徴を有しており、たとえば圧電体、
誘電体、半導体、センサ、オプトエレクトロニクス材な
どの機能性セラミックスの原料として好適に用いられる
。The perovskite oxide powder obtained by the method of the present invention has excellent characteristics as described above, such as piezoelectric materials,
It is suitably used as a raw material for functional ceramics such as dielectrics, semiconductors, sensors, and optoelectronic materials.
し実施例］
次に、実施例により本発明をさらに詳細に説明するが、
本発明はこれらの例によってなんら限定されるものでは
ない。[Example] Next, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited in any way by these examples.
（実施例１）
Ｔｉｅ２換算２７．９７ｇのオキシ硝酸チタンとオキシ
硝酸ジルコニウム２水塩１７３．７２ｙをイオン交換水
３１に溶解させた。この溶液を激しく撹拌しながら、こ
れに室温下で０．５モル／ｌの炭酸アンモニウム水溶液
２．２１を０．１４！／ｍｉｎの速度で添加し、添加終
了後さらに１時間撹拌を続けＡ液を調製した。(Example 1) Titanium oxynitrate (27.97 g in terms of Tie2) and 173.72 y of zirconium oxynitrate dihydrate were dissolved in 31 ion-exchanged water. While vigorously stirring this solution, 0.14 ml of 0.5 mol/l ammonium carbonate aqueous solution was added to it at room temperature. /min, and after the addition was completed, stirring was continued for an additional hour to prepare Solution A.
このＡ液は、無色透明な陽性の水和酸化チタンと水和酸
化ジルコニウムとの混合ヒドロシルであり、このｐＨは
２，２５であった。This solution A was a colorless and transparent positive mixed hydrosil of hydrated titanium oxide and hydrated zirconium oxide, and its pH was 2.25.
一方、２Ｎのアンモニア水４．１０Ｒをホモジナイザを
用いて激しく撹拌しながら、これに、室温下で、硝酸鉛
３０Ｔ、４３ｇと硝酸ランタン６水塩３８．９７．とを
イオン交換水２１に溶解した水溶液を０．２ｆ／ｍｉｎ
の速度で添加し、同時に前記Ａ液を０．５２ｆ／ｍｉｎ
の速度で添加し、添加終了後、さらに１時間撹拌を続け
たのち、−晩静！し、沈殿を形成させた。次にこのスラ
リーを水洗、ろ過したのち、得られた固形物を一晩乾燥
したのち、種々の温度で３時間仮焼し、Ｘ線回折により
、焼成物の結晶相を固定した。その結果、６５０℃以上
で擬似立方晶のＰＬＺＴの単相が形成されることが確認
できた。Meanwhile, while vigorously stirring 4.10 R of 2N ammonia water using a homogenizer, 43 g of 30 T of lead nitrate and 38.97 g of lanthanum nitrate hexahydrate were added to this at room temperature. An aqueous solution of and dissolved in ion exchange water 21 is heated at 0.2 f/min.
At the same time, add the liquid A at a rate of 0.52f/min.
After the addition was complete, stirring was continued for an additional hour, and the temperature was - night! and a precipitate formed. Next, this slurry was washed with water and filtered, and the obtained solid material was dried overnight and then calcined for 3 hours at various temperatures, and the crystal phase of the calcined product was fixed by X-ray diffraction. As a result, it was confirmed that a pseudo-cubic PLZT single phase was formed at temperatures of 650° C. or higher.
（比較例１）
実施例１におけるＡ液の調製の際に、炭酸アンモニウム
水溶液の代りに、ＩＮアンモニア水を用いてｐＨを８．
０まで上昇させた液（水和酸化チタン、水和酸化ジルコ
ニウム混合沈殿物含有）を用いた以外は、実施例１と同
様にして焼成物を得た。そのＸ線回折の結果、７５０℃
以上で擬似立方晶のＰＬＺＴの単相が形成されることが
確認できた。(Comparative Example 1) When preparing Solution A in Example 1, IN ammonia water was used instead of the ammonium carbonate aqueous solution to adjust the pH to 8.
A fired product was obtained in the same manner as in Example 1, except that the liquid (containing a mixed precipitate of hydrated titanium oxide and hydrated zirconium oxide) was used. As a result of the X-ray diffraction, 750℃
As described above, it was confirmed that a single phase of pseudo-cubic PLZT was formed.
実施例１と比較例１との比較から明らかなように、水和
酸化チタンと水和酸化ジルコニウムとの混合ヒドロシル
を用いた場合には、水和酸化チタンと水和酸化ジルコニ
ウムとの混合沈殿物を用いた場合に比べて、１００℃低
い温度で単一相のジルコン酸チタン酸鉛ランタンが形成
する。As is clear from the comparison between Example 1 and Comparative Example 1, when a mixed hydrosil of hydrated titanium oxide and hydrated zirconium oxide is used, a mixed precipitate of hydrated titanium oxide and hydrated zirconium oxide is formed. A single-phase lead lanthanum zirconate titanate is formed at a temperature 100° C. lower than that obtained when using a single-phase lanthanum zirconate titanate.
また、走査型電子顕微鏡による観察の結果、実施例１の
粉末は、平均粒径０．１μｍ、比較例１の粉末は、平均
粒径０．５μｍであり、本発明の優位性が実証された。Furthermore, as a result of observation using a scanning electron microscope, the powder of Example 1 had an average particle size of 0.1 μm, and the powder of Comparative Example 1 had an average particle size of 0.5 μm, demonstrating the superiority of the present invention. .
２ ジルコン タン 。ＰＺＴ の ゛告Ｔ ｉ
Ｏ２換算３５．９６＃のオキシ硝酸チタンとオキシ硝
酸ジルコニウム２水塩１４６．９９ｇとをイオン交換水
３１に溶解したのち、この溶液を激しく撹拌しながら、
これに室温下で０．５モル／ｌの炭酸アンモニウム水溶
液１．８０ｔ’を０．１１７ｍ１ｎの速度で添加し、添
加終了後、さらに１時間撹拌を続けてＣ液を調製した。2 Zircon Tan. PZT's Notice Ti
After dissolving 35.96 # of titanium oxynitrate in terms of O2 and 146.99 g of zirconium oxynitrate dihydrate in 31 ml of ion-exchanged water, while vigorously stirring this solution,
To this was added 1.80 t' of a 0.5 mol/l ammonium carbonate aqueous solution at a rate of 0.117 ml at room temperature, and after the addition was complete, stirring was continued for an additional hour to prepare Solution C.
このＣ液は、無色透明な陽性の水和酸化チタンと酸化ジ
ルコニウムとの混合ヒドロシルであり、そのｐＨは２．
１５であった。This C solution is a colorless and transparent positive mixed hydrosil of hydrated titanium oxide and zirconium oxide, and its pH is 2.
It was 15.
次に、ＩＮアンモニウム水１．５１をホモジナイザを用
いて激しく撹拌しながら、これに硝酸鉛３３７．８３ｙ
をイオン交換水２１に溶解してなるＤ液を０．２Ｚ／ｍ
ｉｎの速度で添加し、同時に前記Ｃ液を０．４１１／ｍ
ｉｎの速度で添加し、添加終了後さらに１時間撹拌を続
は一晩装置し沈殿を形成させた。このスラリーを水洗、
ろ過し、得られた固形物を１２０℃で一晩乾燥したのち
、種々の温度で３時間仮焼し、Ｘ線回折により、焼成物
の結晶相を固定した。その結果、６５０℃以上で立方晶
のＰＺＴの単相が形成することが確認できた。Next, 1.51 y of IN ammonium water was added to 337.83 y of lead nitrate while stirring vigorously using a homogenizer.
0.2Z/m of solution D, which is obtained by dissolving the
At the same time, the C solution was added at a rate of 0.411/m
After the addition was complete, the solution was stirred for an additional hour and then overnight to form a precipitate. Wash this slurry with water,
After filtering and drying the obtained solid substance overnight at 120° C., it was calcined for 3 hours at various temperatures, and the crystal phase of the calcined product was fixed by X-ray diffraction. As a result, it was confirmed that a cubic PZT single phase was formed at 650° C. or higher.
Claims (1)
ＡｌおよびＧａの中から選ばれた少なくとも１種を含有
するペロブスカイト酸化物粉末を湿式法で製造するに当
り、前記金属元素の中から選ばれた少なくとも１種の金
属元素のポリカチオンクリアゾルと、前記以外の金属元
素を含む可溶性金属化合物の水性溶液とを、沈殿形成剤
の存在下に接触させて沈殿を形成させ、次いで該沈殿を
焼成することを特徴とするペロブスカイト酸化物粉末の
製造方法。(1) Constituent metal elements include Ti, Zr, Cr, Fe,
In producing a perovskite oxide powder containing at least one selected from Al and Ga by a wet method, a polycation clear sol of at least one metal element selected from the above metal elements; A method for producing perovskite oxide powder, which comprises contacting an aqueous solution of a soluble metal compound containing a metal element other than the above in the presence of a precipitant to form a precipitate, and then firing the precipitate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5065688A JPH01224210A (en) | 1988-03-03 | 1988-03-03 | Production of perovskite oxide powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5065688A JPH01224210A (en) | 1988-03-03 | 1988-03-03 | Production of perovskite oxide powder |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01224210A true JPH01224210A (en) | 1989-09-07 |
Family
ID=12864993
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5065688A Pending JPH01224210A (en) | 1988-03-03 | 1988-03-03 | Production of perovskite oxide powder |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01224210A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04295012A (en) * | 1990-12-28 | 1992-10-20 | Rhone Poulenc Chim | Compound of especially titanite type and based on especially reduced titanium vanadium or niobium and method of manufacturing same |
| JPH04305017A (en) * | 1990-12-28 | 1992-10-28 | Rhone Poulenc Chim | Compound of especially titanite type and based on especially reduced titanium vanadium or niobium and method of manufacturing same |
-
1988
- 1988-03-03 JP JP5065688A patent/JPH01224210A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04295012A (en) * | 1990-12-28 | 1992-10-20 | Rhone Poulenc Chim | Compound of especially titanite type and based on especially reduced titanium vanadium or niobium and method of manufacturing same |
| JPH04305017A (en) * | 1990-12-28 | 1992-10-28 | Rhone Poulenc Chim | Compound of especially titanite type and based on especially reduced titanium vanadium or niobium and method of manufacturing same |
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