JPS62167217A - Production of lead titanate - Google Patents
Production of lead titanateInfo
- Publication number
- JPS62167217A JPS62167217A JP1076686A JP1076686A JPS62167217A JP S62167217 A JPS62167217 A JP S62167217A JP 1076686 A JP1076686 A JP 1076686A JP 1076686 A JP1076686 A JP 1076686A JP S62167217 A JPS62167217 A JP S62167217A
- Authority
- JP
- Japan
- Prior art keywords
- titanium
- lead
- oxalate
- aqueous solution
- oxalic acid
- 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.)
- Granted
Links
- NKZSPGSOXYXWQA-UHFFFAOYSA-N dioxido(oxo)titanium;lead(2+) Chemical compound [Pb+2].[O-][Ti]([O-])=O NKZSPGSOXYXWQA-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 89
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 23
- 239000002244 precipitate Substances 0.000 claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000001301 oxygen Substances 0.000 claims abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 4
- 239000007864 aqueous solution Substances 0.000 claims description 33
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 claims description 32
- BBJSDUUHGVDNKL-UHFFFAOYSA-J oxalate;titanium(4+) Chemical compound [Ti+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O BBJSDUUHGVDNKL-UHFFFAOYSA-J 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 10
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 7
- 238000007796 conventional method Methods 0.000 abstract description 2
- 238000000197 pyrolysis Methods 0.000 abstract description 2
- 230000002378 acidificating effect Effects 0.000 abstract 5
- 238000005057 refrigeration Methods 0.000 abstract 1
- 239000010936 titanium Substances 0.000 description 25
- 238000000034 method Methods 0.000 description 23
- 239000000843 powder Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 12
- 229910052719 titanium Inorganic materials 0.000 description 12
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 11
- 239000002245 particle Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 238000001556 precipitation Methods 0.000 description 8
- 235000012970 cakes Nutrition 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 238000010304 firing Methods 0.000 description 5
- 239000012452 mother liquor Substances 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- ZASTUNHYSNBLQG-UHFFFAOYSA-N nitric acid oxygen(2-) titanium(4+) Chemical compound [N+](=O)(O)[O-].[O-2].[Ti+4].[O-2] ZASTUNHYSNBLQG-UHFFFAOYSA-N 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- -1 chlorine ions Chemical class 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 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 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 235000021463 dry cake Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- ANBZWDBEKOZNHY-UHFFFAOYSA-N ethanol;oxalic acid Chemical compound CCO.OC(=O)C(O)=O ANBZWDBEKOZNHY-UHFFFAOYSA-N 0.000 description 1
- 238000004442 gravimetric analysis Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- PFPYHYZFFJJQFD-UHFFFAOYSA-N oxalic anhydride Chemical compound O=C1OC1=O PFPYHYZFFJJQFD-UHFFFAOYSA-N 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- PXDRFTPXHTVDFR-UHFFFAOYSA-N propane;titanium(4+) Chemical compound [Ti+4].C[CH-]C.C[CH-]C.C[CH-]C.C[CH-]C PXDRFTPXHTVDFR-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Abstract
Description
【発明の詳細な説明】
本発明はチタン酸鉛の製造方法に関するものである。更
に具体的には本発明は微細な粉末状のチタン酸鉛の前駆
体沈殿をしゅう酸塩として得る方法において、硝酸酸化
チタン水溶液に硝酸酸化チタン１モル当り、約１．５モ
ルのしゅう酸を加えて、チタンのしゅう酸塩を可溶化せ
しめて得たチタン含有水溶液を硝酸酸化チタンと当量の
鉛化合物を含有する水溶液と接触せしめて該前駆体沈殿
を生成せしめることに特徴をもつチタン酸鉛の製造方法
に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing lead titanate. More specifically, the present invention provides a method for obtaining a fine powdery lead titanate precursor precipitate as oxalate, in which approximately 1.5 moles of oxalic acid is added to an aqueous solution of titanium oxide in nitric acid per mole of titanium oxide. In addition, lead titanate is produced by contacting a titanium-containing aqueous solution obtained by solubilizing titanium oxalate with an aqueous solution containing a lead compound in an amount equivalent to titanium nitrate oxide to form the precursor precipitate. The present invention relates to a manufacturing method.
チタン酸鉛は焦電体材料や高周波領域の圧電センサー等
として広く使用されている。また、各種固溶体の出発原
料としても使用されている。Lead titanate is widely used as a pyroelectric material and piezoelectric sensors in the high frequency range. It is also used as a starting material for various solid solutions.
これらの材料の殆んどは、その粉末を焼き固めた焼結体
として製品化されている。その場合の品質は焼結の度合
で著しく左右されるものであり、従って良好な焼結体を
与えるべき原材料として粉体特性の優れた粉末が望まれ
ている。Most of these materials are commercialized as sintered bodies obtained by baking and solidifying their powders. In this case, the quality is significantly influenced by the degree of sintering, and therefore, a powder with excellent powder properties is desired as a raw material for producing a good sintered body.
先兵狭止
チタン酸鉛の製造方法については種々の提案がなされて
いるが、製造方法の特徴別に分類すると、（１） 各
成分の酸化物粉末を混合し、高温に加熱して固相反応で
合成する方法、
（２）鉛およびチタンのしゅう酸塩を沈殿せしめてこれ
を熱分解して合成する方法、
（３）アルコキシドの混合物もしくは複塩を加水分解に
よって各成分元素を共沈せしめ、この共沈加水分解物を
熱分解する方法、
（４）鉛およびチタンのしゅう酸塩の沈殿合成時にエタ
ノールやプロパツールなどのアルコール類を共存させる
方法、
（５）鉛の酸化物を合成し、これをチタン化合物と水熱
反応せしめる方法、
などをその代表例として挙げることができる。Various proposals have been made regarding the manufacturing method of lead titanate, but the manufacturing methods can be categorized according to their characteristics: (1) oxide powders of each component are mixed, heated to high temperature, and subjected to solid phase reaction; (2) A method of precipitating oxalate of lead and titanium and thermally decomposing the same. (3) A method of co-precipitating each component element by hydrolyzing a mixture or double salt of alkoxide. (4) A method of coexisting alcohols such as ethanol and propatool during the precipitation synthesis of lead and titanium oxalate; (5) A method of synthesizing lead oxide and Typical examples include a method in which titanium is subjected to a hydrothermal reaction with a titanium compound.
しかしながら、これらの方法にもそれぞれ何等かの問題
点があり、不断の改良研究が継続されている。However, each of these methods has some problems, and continuous improvement research is being continued.
本発明者らは（２）のしゅう酸塩法及び（４）のしゅう
酸−アルコール法に着目して一連の技術改良を成し遂げ
て来た。The present inventors have achieved a series of technical improvements by focusing on (2) the oxalate method and (4) the oxalic acid-alcohol method.
本発明者らおよび山村は、（４）のしゅう酸−エタノー
ル法で合成されるチタン酸塩の仮焼粉末の融着現象が、
出発原料イオンの混合水溶液中に少量残存する塩素イオ
ンに起因していることを見出し、塩素イオン濃度を所定
値以下に下げることで融着を抑止できることを見出した
（特願昭６０−１３９１０号明細書）。The present inventors and Yamamura discovered that the fusion phenomenon of calcined titanate powder synthesized by the oxalic acid-ethanol method (4)
They found that this is caused by a small amount of chlorine ions remaining in the mixed aqueous solution of starting material ions, and found that fusion can be suppressed by lowering the chlorine ion concentration to a predetermined value or less (Japanese Patent Application No. 13910/1982). book).
更に、本発明者らは、使用するエタノール量を激減せし
めることで製造コストを著しく低下せしめ得る方法（特
願昭６０−７７２３４号明細書）や、エタノールをイン
プロパツール及びノルマルプロパツールに代替して更に
製造コストを低減する方法（特願昭６０−７７’ ２３
５号明細書）を提示した。Furthermore, the present inventors have developed a method that can significantly reduce manufacturing costs by drastically reducing the amount of ethanol used (Japanese Patent Application No. 77234/1982), and a method of replacing ethanol with in-proper tool and normal-proper tool. A method for further reducing manufacturing costs (Patent Application 1986-77'23
Specification No. 5) was presented.
〒 ′符における問題点と解“策
本発明者らは、しゅう酸・アルコール系でのチタン酸鉛
を含むペロブスカイト型酸化物の前駆体合成の各種改良
方法のいずれにおいても沈殿構成元素の存在比率の制御
が重要な課題であることに注目し、鋭意検討を加えて以
下のような新しい方法を提案して来た。〒 ``Problems and Solutions for ``Measures'' The present inventors have investigated the abundance ratio of precipitate constituent elements in all of the various improved methods for synthesizing precursors of perovskite-type oxides containing lead titanate in an oxalic acid/alcohol system. Focusing on the important issue of controlling
しゅう酸塩沈殿中に塩素を含有しないようにする為には
、可溶性塩として硝酸塩を選ぶことが好まれる。この場
合、Ｔｉが反応後再溶解する現象が起きる。In order to avoid the inclusion of chlorine in the oxalate precipitation, it is preferred to choose nitrate as the soluble salt. In this case, a phenomenon occurs in which Ti is redissolved after the reaction.
Ｔｉの水溶液への再溶解現象についてはしゅう酸塩共沈
物の生成で母液中に高濃度の硝酸が生じ、これが例えば
しゅう酸チタニル鉛と反応して次式に従って多量のＴｉ
を母液中に残存させる可能性が和久らの研究（電気通信
研究所・研究実用化報告別冊２８号（１９７５））など
で知られている。Regarding the redissolution phenomenon of Ti in an aqueous solution, a high concentration of nitric acid is generated in the mother liquor due to the formation of oxalate coprecipitate, which reacts with, for example, titanyl lead oxalate, and a large amount of Ti is dissolved according to the following equation.
It is known from the research of Kazuhisa et al. (Telecommunications Research Institute, Research and Practical Application Report Special Issue No. 28 (1975)) that it is possible to cause the remaining in the mother liquor.
ＰｂＴｉ０（Ｃｚ ０ａ）ｚ ＋２ＨＮＯ３→Ｐ ｂ
Ｃ２Ｏａ ＋ Ｔ ｉ Ｏ（Ｎ ０３）ｚ ＋ ＨｚＣ
２０４この現象を回避する為に、本発明者らは特願昭６
０−７７２３６号明細書において、反応生成液中へ乾燥
アンモニアガスを吹き込む方法を提示した。該方法によ
って構成元素の存在比率を制御することが可能となった
。PbTi0(Cz 0a)z +2HNO3→P b
C2Oa + T i O(N 03)z + HzC
204 In order to avoid this phenomenon, the present inventors filed a patent application in
No. 0-77236 proposed a method of blowing dry ammonia gas into the reaction product liquid. This method made it possible to control the abundance ratio of the constituent elements.
更に、本発明者らは炭素数が４から１５のアルコールを
用いてペロブスカイト型酸化物の前駆体としてのしゅう
酸塩沈殿反応を硝酸鉛と硝酸酸化チタンを含む水溶液に
ついて試みたところ、仕込み原料で設定したＴ ｉ ／
Ｐ ｂ比（原子比）が、沈殿を焼成して得られたＰｂ
Ｔｉ０＋においてほぼ完全に再現されるという、エタノ
ールやプロパツールでは求め得なかった予想外の良好な
結果が得られることを開示した（特願昭６０−７７２３
７号明細書）。Furthermore, the present inventors attempted an oxalate precipitation reaction as a precursor of a perovskite-type oxide using an alcohol having a carbon number of 4 to 15 on an aqueous solution containing lead nitrate and titanium nitrate oxide, and found that the raw materials used were The set T i /
The Pb ratio (atomic ratio) is the Pb obtained by firing the precipitate.
It was disclosed that an unexpectedly good result that could not be obtained with ethanol or propatool could be obtained, which was almost completely reproduced with Ti0+ (Patent Application No. 7723/1983).
7 specification).
該方法に開示した条件下では上記効果が確認されたが、
しゅう酸添加終了後も長時間攪拌を継続したり、濾過操
作に長時間を要したりした場合にはＴｉの再溶解がおき
ることがその後の検討で見出され、生成沈殿の経時安定
性に問題点のあることが判った。Although the above effects were confirmed under the conditions disclosed in the method,
Subsequent studies have found that if stirring is continued for a long time after the addition of oxalic acid is finished, or if the filtration operation takes a long time, re-dissolution of Ti will occur, and this will affect the stability of the formed precipitate over time. It turned out that there was a problem.
本発明者らはしゅう酸塩沈殿の反応液中での安定性を確
保すべく鋭意検討を加えたところ、アルコール共存系に
おいてはしゅう酸塩の沈殿に関して従来一般則として認
められていた、しゅう酸／Ｔｉ＝１／１（モル比）なる
量論比ではなく、しゅう酸／Ｔｉ−１／２（モル比）な
る量論比において定量的な沈殿形成がなされる事実を先
行特許出Ｗｉ（特願昭６０−２１１７０４号明細書）に
て開示した。該出願においてエタノールやプロパツール
などを添加しない水溶液中ではＴｉのしゅう酸塩沈殿の
回収率は最高でも６５重景％であり、水溶液中の硝酸酸
化チタンの濃度の増加とともに回収率が著しく低下する
ことを開示した。The present inventors conducted extensive studies to ensure the stability of oxalate precipitation in the reaction solution, and found that oxalate, which was previously accepted as a general rule regarding precipitation of oxalate in an alcohol-coexisting system, The fact that a quantitative precipitate is formed at the stoichiometric ratio of oxalic acid/Ti-1/2 (molar ratio) rather than the stoichiometric ratio of /Ti = 1/1 (molar ratio) was disclosed in the prior patent publication Wi (Special It was disclosed in Japanese Patent Application No. 60-211704). In this application, the recovery rate of Ti oxalate precipitation in an aqueous solution without the addition of ethanol or propatool is at most 65%, and the recovery rate decreases significantly as the concentration of titanium nitrate oxide in the aqueous solution increases. I disclosed that.
本発明者らは水溶液中の硝酸酸化チタンからのしゅう酸
塩の挙動について更に詳しく検討を加えたところ、硝酸
鉛と硝酸酸化チタンが共存する水溶液に、Ｐｂ１モルに
対してしゅう酸１モル、Ｔｉ１モルに対して理論量とし
てしゅう酸０．５モルの比率を保持するしゅう酸水溶液
を接触せしめる時にはｐｂとＴｉの存在比率が略１：１
の沈殿を形成し得ることを見出し、先願発明（特願昭６
０−２１１７０５号明細書）を完成した。The present inventors conducted a more detailed study on the behavior of oxalate from titanium nitrate oxide in an aqueous solution, and found that in an aqueous solution in which lead nitrate and titanium nitrate oxide coexist, 1 mol of oxalate per 1 mol of Pb, 1 mol of Ti1 When brought into contact with an oxalic acid aqueous solution that maintains a ratio of 0.5 mol of oxalic acid as a theoretical amount to mol, the abundance ratio of PB and Ti is approximately 1:1.
It was discovered that it is possible to form a precipitate of
0-211705) was completed.
本発明者らは先願の２発明で開示した硝酸酸化チタンか
らのしゅう酸塩の沈殿生成挙動に関して更に詳しく検討
を加え、硝酸酸化チタン水溶液中の硝酸酸化チタン１モ
ルに対して１モル以上、好ましくは１．５モル程度のし
ゅう酸を加えると、硝酸酸化チタンは長期間に亘って非
常に安定な水に可溶なしゅう酸塩化合物に転化すること
を見出した。The present inventors conducted a more detailed study on the precipitation formation behavior of oxalate from titanium nitrate oxide disclosed in the two previous inventions, and found that 1 mol or more of oxalate per 1 mol of titanium nitrate oxide in an aqueous solution of titanium nitrate oxide, It has been found that by adding preferably about 1.5 moles of oxalic acid, the titanium nitrate oxide is converted to a water-soluble oxalate compound which is very stable over a long period of time.
沈殿として析出することを見出した。It was found that it precipitates as a precipitate.
しゅう酸の理論添加量を鉛１モル及びチタン１モルに対
して１．５モルとした時に形成される共沈殿物はチタン
酸鉛の前駆体沈殿として望ましい特性を有することを見
出して、本発明を完成するに至った。It has been discovered that the coprecipitate formed when the theoretical addition amount of oxalic acid is 1.5 mol per mol of lead and 1 mol of titanium has desirable characteristics as a precursor precipitate of lead titanate, and the present invention I was able to complete it.
オ虜」坏す１見性
本発明は、硝酸酸化チタンの水溶液にしゅう酸を添加す
ると、硝酸酸化チタン１モル当り１モル以上好ましくは
１．５モルのしゅう酸を添加したものが、水溶液中にお
いて極めて安定な可溶性化合物を形成するという新規な
発見に基盤をもつ。理論モル量論比をＴ ｉ ／ Ｐ
ｂ ＝ １ ／ １ 、 Ｌゆう酸／（Ｔｉ＋Ｐｂ）＝
１．５に設定した、しゅう酸可溶化チタン水溶液と硝酸
鉛水溶液との反応で得られるチタン酸鉛前駆体沈殿を焼
成して得られるチタン酸鉛粉末において、Ｔ ｉ ／
Ｐ ｂ ＝ １ ／ １の元素存在比を保持し得るとい
う発見にも新規性がある。According to the present invention, when oxalic acid is added to an aqueous solution of titanium nitrate oxide, 1 mol or more preferably 1.5 mol of oxalic acid is added to the aqueous solution per 1 mol of titanium nitrate oxide. It is based on the novel discovery that it forms extremely stable soluble compounds. The theoretical molar stoichiometric ratio is T i / P
b = 1 / 1, L oxalic acid / (Ti + Pb) =
T i /
The discovery that the element abundance ratio of P b = 1/1 can be maintained is also novel.
更には、反応温度２０℃で合成した該前駆体を１１０℃
で乾燥した後のＸ線回折、螢光Ｘ線回折１、元素分析、
示差熱重量分析、熱分解ガスの質量分析、ラマンスペク
トル分析等による解析に基いて、乾燥前駆体沈殿は
Ｐｔ）ＣｔＯａと（Ｔ ｉ ０）ｚ（ＮＯ３）（ＯＨ）
ＣｚＯ４とから成り立つことを示唆できる点においても
発明の新規性がある。Furthermore, the precursor synthesized at a reaction temperature of 20°C was heated to 110°C.
X-ray diffraction after drying, fluorescent X-ray diffraction 1, elemental analysis,
Based on analysis by differential thermogravimetry, mass spectrometry of pyrolysis gas, Raman spectroscopy, etc., the dried precursor precipitate is composed of Pt)CtOa and (T i 0)z(NO3)(OH).
The invention is also novel in that it can be suggested that it is composed of CzO4.
四−玉 本発明の方法に従えば、次のような効果が期待できる。Four balls If the method of the present invention is followed, the following effects can be expected.
（１１チタン／しゅう酸＝１／１．５（モル比）の化合
物は水溶液中にて極めて安定であり、室温下数週間密栓
放置しても変化を生じない。従って、本発明者らが先行
特許出願にて実施して来た硝酸酸化チタン水溶液の冷蔵
密栓貯蔵および調製後７−１０日以内での使用という従
来法での制約がまったく不要となる。(11 The compound of titanium/oxalic acid = 1/1.5 (molar ratio) is extremely stable in an aqueous solution, and does not change even if left in a sealed container at room temperature for several weeks. Therefore, the present inventors There is no need for the conventional method of storing an aqueous solution of titanium nitrate oxide in a sealed container in a refrigerated container and using it within 7 to 10 days after preparation, which was implemented in the patent application.
（２） 硝酸酸化チタン水溶液を５０℃以上に加熱し
て攪拌すると３０分程で分解反応をおこして白色沈殿を
形成する為、本発明者らの先行出願においては、反応温
度の上限を４０℃という比較的長時間に亘って硝酸酸化
チタンが安定に存在し得る点に設定せざるを得なかった
が、本発明の方法によれば、硝酸鉛水溶液の温度はその
沸点近くまで高めることが可能であり、該可溶性化合物
も５０−８０℃の加温条件下でも比較的長時間にわたっ
て安定なので、３０−１００℃の反応温度も容易に設定
できる。(2) When a titanium nitrate oxide aqueous solution is heated to 50°C or higher and stirred, a decomposition reaction occurs in about 30 minutes and a white precipitate is formed. Therefore, in the inventors' previous application, the upper limit of the reaction temperature was set at 40°C. However, according to the method of the present invention, the temperature of the lead nitrate aqueous solution can be raised to near its boiling point. Since the soluble compound is also stable for a relatively long period of time even under heating conditions of 50-80°C, the reaction temperature of 30-100°C can be easily set.
（３） 生成した沈殿の母液への再溶解の恐れがない
ので、反応時間、濾過時間等を工業生産レベルで最適領
域に設定することができる。(3) Since there is no fear that the generated precipitate will be redissolved in the mother liquor, the reaction time, filtration time, etc. can be set in the optimum range at the industrial production level.
鉛は塩化物以外の塩、特に硝酸塩として供給されること
が好ましい。酢酸鉛や蟻酸鉛等も用いることができる。Preferably, the lead is supplied as a salt other than chloride, especially as a nitrate. Lead acetate, lead formate, etc. can also be used.
硝酸鉛の水溶液中濃度は０．０１−０．５モル／１、好
ましくは０．０５−０．３モル／ｌに設定することがで
きる。The concentration of lead nitrate in the aqueous solution can be set at 0.01-0.5 mol/1, preferably 0.05-0.3 mol/l.
共−迭
チタン酸鉛の前駆体沈殿は好ましくは硝酸鉛の水溶液に
、しゅう酸で可溶化したチタン含有水溶液を接触せしめ
ることで鉛およびチタンのしゅう酸塩の共沈殿体として
得られる。The co-precipitated lead titanate precursor is preferably obtained as a coprecipitate of lead and titanium oxalate by contacting an aqueous solution of lead nitrate with an aqueous solution containing titanium solubilized with oxalic acid.
本発明の達成に必要なしゅう酸は硝酸酸化チタン水溶液
に所要量を全量添加することができるが、硝酸鉛水溶液
からしゅう酸鉛が析出しない範囲内かつしゅう酸可溶化
チタン水溶液の安定性を損わない範囲内で所要量の一部
を予め硝酸鉛水溶液中に添加せしめる方法を用いること
もできる。The required amount of oxalic acid required to achieve the present invention can be added to the titanium oxide nitric acid aqueous solution in its entirety, but within a range in which lead oxalate does not precipitate from the lead nitrate aqueous solution and does not impair the stability of the oxalic acid solubilized titanium aqueous solution. It is also possible to use a method in which a part of the required amount is added in advance to the lead nitrate aqueous solution within a range that does not exceed the above.
硝酸酸化チタン水溶液中のＴｉ濃度は０．０１−３モル
／１好ましくは０．０５−１モル／１の範囲でとること
ができる。The Ti concentration in the aqueous titanium nitrate oxide solution can be set in the range of 0.01-3 mol/1, preferably 0.05-1 mol/1.
硝酸酸化チタン水溶液への所定量のしゅう酸の添加は、
しゅう酸無水物又はしゅう酸２水和物を常温もしくは１
０℃近傍に冷却した硝酸酸化チタン水溶液へゆっくりと
加えてもよいし、しゅう酸水溶液を加える方法を用いて
もよい。初期段階では沈殿が形成されるが所定量の１／
３を越えた時点から沈殿量の減少が始まり、全量投入に
よって完全な均一溶液が形成される。しゅう酸の投入量
は、理論量としてチタン／しゅう酸（モル１モル）＝１
／１．５であるが、本発明にいうチタン／しゅう酸（モ
ル１モル）＝ｌ／約１．５とは、このモル比が１／１．
４７〜１／１．５３であることが好ましく、更に該モル
比が１／１．４８５〜１／１．５１５であることがより
好ましいことを意味するものである。但し、この量比が
例えば１ ／ １．６になれば、生成する沈殿において
Ｔ ｉ ／ Ｐ ｂ ＜ １となり、焼成して得られる
チタン酸鉛は本発明が目標とする低温での焼成温度域（
〜８００℃）では、鉛過剰の赤色酸化物を与えるととも
に、個々の粒子の成長と相互融着現象をもたらす。Addition of a predetermined amount of oxalic acid to a nitric acid titanium oxide aqueous solution is as follows:
Oxalic acid anhydride or oxalic acid dihydrate at room temperature or
It may be added slowly to a titanium oxide nitric acid aqueous solution cooled to around 0° C., or a method of adding an oxalic acid aqueous solution may be used. At the initial stage, a precipitate is formed, but 1/2 of the predetermined amount
The amount of precipitate begins to decrease when the amount exceeds 3, and a completely homogeneous solution is formed by adding the entire amount. The amount of oxalic acid added is the theoretical amount of titanium/oxalic acid (1 mole) = 1
/1.5, but titanium/oxalic acid (1 mole) = l/about 1.5 in the present invention means that this molar ratio is 1/1.
This means that the molar ratio is preferably 47 to 1/1.53, and more preferably 1/1.485 to 1/1.515. However, if this quantitative ratio is, for example, 1/1.6, T i / P b < 1 in the generated precipitate, and the lead titanate obtained by firing falls within the low-temperature firing temperature range targeted by the present invention. (
~800° C.) gives a red oxide with an excess of lead, as well as the growth of individual grains and interfusion phenomena.
一方この量比が１．４７未満の場合には反応収率の低下
が大となる。On the other hand, if this quantitative ratio is less than 1.47, the reaction yield will decrease significantly.
反応温度は硝酸鉛水溶液の硝酸鉛析出温度近傍から沸点
近傍迄の任意の温度を選ぶことができる。The reaction temperature can be selected from any temperature from around the lead nitrate precipitation temperature of the lead nitrate aqueous solution to around the boiling point.
例えば０℃から１００℃の反応温度を選ぶことができる
。For example, a reaction temperature of 0°C to 100°C can be chosen.
チタンのしゅう酸塩溶液は、０℃近傍から８０℃付近ま
での温度を選ぶことができるが、好ましくは常温から５
０℃を選ぶことができる。The temperature of the titanium oxalate solution can be selected from around 0°C to around 80°C, but preferably from room temperature to 5°C.
You can choose 0℃.
反応は硝酸鉛水溶液を所定の液温に保持して激しく攪拌
している中に、チタンのしゅう酸塩溶液を所定温度のも
とで滴下することで進めることができる。The reaction can proceed by dropping the titanium oxalate solution dropwise at a predetermined temperature while the aqueous lead nitrate solution is maintained at a predetermined temperature and vigorously stirred.
滴下終了後直ちに濾過操作に入ってもよいが、後反応を
適切な時間おこなった後に濾過操作に入ることもできる
。The filtration operation may be started immediately after the completion of the dropwise addition, but it is also possible to start the filtration operation after performing a post-reaction for an appropriate period of time.
υ
沈殿をが過によって分別し、口色ケーキを得、反応によ
って生成した硝酸を除くためにも、水で適切な洗浄を行
って沈殿中に残留する母液を可能な限り取り除いてから
洗液を炉別して白色ケーキを得ることができる。洗浄回
数は適宜定めることができる。υ The precipitate is separated by filtration to obtain a pale-colored cake, and in order to remove the nitric acid produced by the reaction, the washing solution is washed with water to remove as much of the mother liquor remaining in the precipitate as possible. A white cake can be obtained by furnace separation. The number of times of washing can be determined as appropriate.
得られた白色ケーキは乾燥後、砕解してペロプスカイト
型酸化物前駆体粉体とする。この段階で懺
の砕解は、後に続く１焼に際して、適切な量の酸素の流
通を確保する上で重要である。なお〜乾燥ケーキは弱い
磨砕力で容易に微粉化できるし、この段階で粒子を完全
分散状態にする必要もないので、砕解手段からの不純物
の混入の恐れはない。The obtained white cake is dried and then crushed to obtain a perovskite-type oxide precursor powder. The crushing of the slag at this stage is important in ensuring the flow of an appropriate amount of oxygen during the subsequent firing. Note that the dry cake can be easily pulverized by a weak grinding force, and there is no need to completely disperse the particles at this stage, so there is no risk of contamination with impurities from the pulverizing means.
退
１０００℃、で１焼する。このか焼温度は低温であるこ
とが望ましいが、重量変化が最早認められ炉
ない温度で４焼を行なうことが必要である。５００−８
００℃での１焼が鉛の昇華をより少なく抑制する上でも
好ましい。Bake at 1000℃ for 1 time. Although it is desirable that the calcination temperature be low, it is necessary to carry out the fourth calcination at a temperature that does not cause any weight change to be observed. 500-8
Baking at 00°C is also preferable in terms of suppressing sublimation of lead.
イ゛焼は酸素の存在下でおこなうことが必要であるが、
マツフル炉のような強制流通機構を有しなとることがで
きるが好ましくは０．５−２０℃／分をとることができ
る。しゅう酸塩の分解が終る４００℃近傍までの昇温速
度は余り大きくとらない方が好ましい。It is necessary to carry out firing in the presence of oxygen,
A forced flow mechanism such as a Matsufuru furnace can be used, but preferably the flow rate can be 0.5-20°C/min. It is preferable that the rate of temperature increase up to around 400° C., at which the decomposition of oxalate ends, is not too high.
以下実験例をもって本発明の内容を更に具体的に説明す
る。The content of the present invention will be explained in more detail below using experimental examples.
叉慧炭
実施例１
市販のテトライソプロピルチタン２５０＋＋＋Ｉｌを蒸
留水３５００ｍｊ！に滴下して水酸化物を得、これを濾
過した後、純水５００１１１で３回洗浄を繰返して水酸
化チタンを得た。これを氷冷した市販特級濃硝酸１００
ｍｊ！に加え、昼夜放置後濾過して、硝酸酸化チタン溶
液を得た。Ｔｉ濃度をＴｉ（ｈとして重量分析法で決定
して、０．１２５７ ｇ −Ｔｉ／ｍｊ！の結果が得ら
れた。硝酸酸化チタン溶液２０ｍＪを純粋２４３ｎ＋１
に混合し、これにしゅう酸２永和物（純度９９．５％）
９．９７９ｇを室温にて溶かしてチタン濃度０．２モル
／１、Ｔｉ／（ＣＯＯ’Ｈ） ｔ ＝ １／ １．５
（モル１モル）の水溶液を得た。Charcoal Example 1 Commercially available tetraisopropyl titanium 250 +++ Il was mixed with 3500 mj of distilled water! was added dropwise to obtain hydroxide, which was filtered and washed three times with pure water 500111 to obtain titanium hydroxide. Commercially available special grade concentrated nitric acid 100
mj! In addition, the solution was left to stand for a day and night and then filtered to obtain a titanium oxide nitric acid solution. The Ti concentration was determined by gravimetric analysis as Ti (h), and a result of 0.1257 g -Ti/mj! was obtained.
Mix this with oxalic acid dihydrate (purity 99.5%)
Melt 9.979g at room temperature, titanium concentration 0.2 mol/1, Ti/(COO'H) t = 1/ 1.5
An aqueous solution of (1 mol) was obtained.
市販の特級硝酸鉛（純度９９．５％）１７．４７８ｇを
純水２６３ｎｌに溶かして鉛濃度０．２モル／ｌの反応
液を調製し８５℃に保持し、激しく攪拌している中に室
温に保持された該水溶液を滴下炉斗を用いて、１０ｍｊ
！／分の速度で滴下した。更に８５℃の湯浴中、７９℃
から８２℃の液温で２時間攪拌し、反応を完結せしめた
。３８℃迄冷却した後ブフナーが斗を用いて母液を吸引
濾過して白色ケーキを得た。A reaction solution with a lead concentration of 0.2 mol/l was prepared by dissolving 17.478 g of commercially available special grade lead nitrate (purity 99.5%) in 263 nl of pure water. Using a dropping furnace, the aqueous solution held in
! It was added dropwise at a rate of 1/min. Further, in a hot water bath at 85°C, 79°C
The reaction was completed by stirring for 2 hours at a liquid temperature of 82°C. After cooling to 38° C., the mother liquor was suction filtered using a Buchner funnel to obtain a white cake.
得られた白色ケーキを純水２６３ｎ＋ｊ！に投入して砕
解・洗浄を１５分間行ない、ブフナーが斗を用いて洗液
を分離した。この操作を３回繰返して白色ケーキを得た
。Pour the resulting white cake into pure water 263n+j! The mixture was crushed and washed for 15 minutes, and Buchner separated the washing liquid using a funnel. This operation was repeated three times to obtain a white cake.
得られた白色ケーキを１１０℃で１６時間空気浴オーブ
ン中で乾燥した後、メノウ乳鉢で砕解して、チタン酸鉛
前駆体粉末を得た。The obtained white cake was dried in an air bath oven at 110° C. for 16 hours, and then crushed in an agate mortar to obtain a lead titanate precursor powder.
皿里生班末皇定且
前駆体粉末がどの様な化合物から成り立っているかを種
々の分析手段によって調べた。By using various analytical methods, we investigated what kind of compounds the precursor powder was composed of.
前駆体粉末をＸ線回折にて分析したところしゆう酸鉛の
存在が確認された。チタンに由来する化合物の同定はで
きなかった。Analysis of the precursor powder by X-ray diffraction confirmed the presence of lead oxalate. No compounds derived from titanium could be identified.
前駆体粉末を空気流通下、１０℃／分の速度で昇温して
熱重量分析に供したところ、８００℃までの昇温で仕込
み重量に対して３１．７重量％の重量減少が認められた
。When the precursor powder was heated at a rate of 10°C/min under air circulation and subjected to thermogravimetric analysis, a weight loss of 31.7% by weight relative to the charged weight was observed when the temperature was raised to 800°C. Ta.
前駆体粉末をＨｅ流通下、１０℃／分の速度で昇温分解
し脱離ガスの質量分析を行なった（ＱＭＡＳＳ）ところ
、Ｎ Ｏｘの発生が確認された。また、前駆体粉末の元
素分析によって、鉛１原子に比して炭素３．２原子、窒
素０．２９原子の存在比を認めた。When the precursor powder was heated and decomposed at a rate of 10° C./min under He flow, and the desorbed gas was subjected to mass spectrometry (QMASS), the generation of NOx was confirmed. Furthermore, elemental analysis of the precursor powder revealed an abundance ratio of 3.2 atoms of carbon and 0.29 atoms of nitrogen to 1 atom of lead.
前駆体粉末をラマン分光に供したところ、結合ＮＯ８に
由来するピークの存在が確認され、その存在量は先行特
許出願（特願昭６０−２１１７０４号明細書において（
Ｔ ｉ Ｏ）ｚ （Ｎ ０３）２ Ｃｔ ０４の存在が
推察されたチタン酸鉛前駆体で認められたピーク高さの
略１／２であった。When the precursor powder was subjected to Raman spectroscopy, the presence of a peak derived from bonded NO8 was confirmed, and its abundance was reported in the previous patent application (Japanese Patent Application No. 60-211704).
The peak height was approximately 1/2 of the peak height observed in the lead titanate precursor in which the presence of T i O) z (N 03) 2 Ct 04 was presumed.
上記各種分析結果を総合的に結びつけると、本発明の方
法で得られる前駆体粉末は、
ＰｂＣｚＯａと（Ｔ ｉ ０）Ｚ（Ｎ ０３）（ＯＨ）
Ｃ２Ｏ４なる組成物の共沈殿体から形成されている可
能性が高いことが推察された。Comprehensively combining the above various analysis results, the precursor powder obtained by the method of the present invention has the following properties: PbCzOa and (T i 0) Z (N 03) (OH)
It was inferred that there is a high possibility that it was formed from a coprecipitate of the composition C2O4.
ＰｂＴｉ０：＋の合
前駆体粉末をマツフル炉で１．５℃／分の昇温速度で７
００℃に昇温し、２時間保持後徐冷し、目的とする酸化
物を仕込み原料を基準として９４重量％の収率で得た。PbTi0:+ synthesis precursor powder was heated in a Matsufuru furnace at a heating rate of 1.5°C/min.
The temperature was raised to 00°C, maintained for 2 hours, and then slowly cooled to obtain the desired oxide in a yield of 94% by weight based on the charged raw materials.
螢光Ｘ線回折法で酸化物のＴ ｉ ／ Ｐ ｂ比（原子
比）１．００を得た。Ｘ線回折によって正方晶ＰｂＴｉ
０ｚの生成のみが確認され、その結晶粒径は２８０人で
あった。ＢＥＴ法表面積は２．７ｎ（／ｇであった。こ
れより平均粒径０．２８μｍが求められた。The Ti/Pb ratio (atomic ratio) of the oxide was obtained by fluorescence X-ray diffraction method of 1.00. Tetragonal PbTi by X-ray diffraction
Only the formation of 0z was confirmed, and its crystal grain size was 280. The BET method surface area was 2.7 n(/g). From this, an average particle size of 0.28 μm was determined.
該酸化物を超音波振動装置を用いて水中に分散せしめ、
マイクロトラックＤＲ粒度分析計で粒度分布を測定し、
第１図に示す結果を得た。超音波振動装置で酸化物を水
中に分散し、走査型電子顕微鏡で粒子形状を観察したと
ころ、０．１〜０．２μｍの粒子から成り立っているこ
とが判った。これらの粒子がところどころ弱く結合して
いるものが多く観察された。Dispersing the oxide in water using an ultrasonic vibration device,
Measure the particle size distribution with a Microtrac DR particle size analyzer,
The results shown in FIG. 1 were obtained. When the oxide was dispersed in water using an ultrasonic vibrator and the particle shape was observed using a scanning electron microscope, it was found that the particles were composed of particles of 0.1 to 0.2 μm. Many of these particles were observed to be weakly bonded in places.
第１図は、Ｐ ｂ Ｔ ｉ Ｏ３の粒子の粒度分布を示
す図である。FIG. 1 is a diagram showing the particle size distribution of P b T i O3 particles.
Claims (1)
、約１．５モルのしゅう酸を加えて、チタンのしゅう酸
塩を可溶化せしめて得たチタン含有水溶液を硝酸酸化チ
タンと当量の鉛化合物を含有する水溶液と接触せしめて
チタン酸鉛の前駆体沈殿を生成せしめたる後、該前駆体
沈殿を酸素雰囲気にて熱分解することを特徴とするチタ
ン酸鉛の製造方法。1. Add about 1.5 mol of oxalic acid per 1 mol of titanium nitrate oxide to a titanium nitrate oxide aqueous solution to solubilize the titanium oxalate. A method for producing lead titanate, which comprises contacting with an aqueous solution containing lead titanate to form a precursor precipitate of lead titanate, and then thermally decomposing the precursor precipitate in an oxygen atmosphere.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1076686A JPS62167217A (en) | 1986-01-21 | 1986-01-21 | Production of lead titanate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1076686A JPS62167217A (en) | 1986-01-21 | 1986-01-21 | Production of lead titanate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62167217A true JPS62167217A (en) | 1987-07-23 |
| JPH0559846B2 JPH0559846B2 (en) | 1993-09-01 |
Family
ID=11759449
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1076686A Granted JPS62167217A (en) | 1986-01-21 | 1986-01-21 | Production of lead titanate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62167217A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4929436A (en) * | 1987-03-26 | 1990-05-29 | Solvay & Cie (Societe Anonyme) | Process for the manufacture of a powder of mixed metal oxides, and mixed metal oxide powders |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0717443U (en) * | 1993-08-31 | 1995-03-28 | 株式会社ディスコ | Blade auto changer |
-
1986
- 1986-01-21 JP JP1076686A patent/JPS62167217A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4929436A (en) * | 1987-03-26 | 1990-05-29 | Solvay & Cie (Societe Anonyme) | Process for the manufacture of a powder of mixed metal oxides, and mixed metal oxide powders |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0559846B2 (en) | 1993-09-01 |
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