JPH01298023A - Method for synthesizing plzt - Google Patents
Method for synthesizing plztInfo
- Publication number
- JPH01298023A JPH01298023A JP63125835A JP12583588A JPH01298023A JP H01298023 A JPH01298023 A JP H01298023A JP 63125835 A JP63125835 A JP 63125835A JP 12583588 A JP12583588 A JP 12583588A JP H01298023 A JPH01298023 A JP H01298023A
- Authority
- JP
- Japan
- Prior art keywords
- precipitate
- plzt
- oxine
- soln
- solution
- 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
- 238000000034 method Methods 0.000 title claims description 20
- 230000002194 synthesizing effect Effects 0.000 title claims description 11
- 239000002244 precipitate Substances 0.000 claims abstract description 54
- 239000000203 mixture Substances 0.000 claims abstract description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 10
- 239000002738 chelating agent Substances 0.000 claims abstract description 9
- 229910000464 lead oxide Inorganic materials 0.000 claims abstract description 5
- 150000003608 titanium Chemical class 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract 2
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract 2
- 150000003754 zirconium Chemical class 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 24
- 239000013522 chelant Substances 0.000 claims description 11
- 150000004880 oxines Chemical group 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 238000001308 synthesis method Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000010304 firing Methods 0.000 claims description 5
- 239000012266 salt solution Substances 0.000 claims description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 abstract description 22
- 150000003839 salts Chemical class 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 6
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 abstract description 5
- 239000010936 titanium Substances 0.000 abstract description 3
- 238000001354 calcination Methods 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract 2
- 229910020279 Pb(Zr, Ti)O3 Inorganic materials 0.000 abstract 1
- 239000003153 chemical reaction reagent Substances 0.000 description 23
- 150000002500 ions Chemical class 0.000 description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
- 239000000843 powder Substances 0.000 description 10
- 239000013078 crystal Substances 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 229910021645 metal ion Inorganic materials 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000000470 constituent Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000013081 microcrystal Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- -1 ``b'' Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- ZXNIRGPMYQWIJS-UHFFFAOYSA-O azanium azane nitrate Chemical compound [N+](=O)([O-])[O-].[NH4+].N ZXNIRGPMYQWIJS-UHFFFAOYSA-O 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical class O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野コ
本発明は、キレート剤を用いたＰＬＺＴの合成方法に関
する。特に、高い均一性と易焼結性を有するＰＬＺＴ材
料の合成方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for synthesizing PLZT using a chelating agent. In particular, the present invention relates to a method for synthesizing PLZT material with high uniformity and easy sinterability.
［従来の技術］
Ｐｂ（Ｚｒ、Ｔｉ）Ｏ，にＬａを添加した系のＰＬＺＴ
は、透明焼結体にすることができ、電気−光学変換素ｔ
として用いられている。そのようなＰ ＬＺＴ結晶体を
調製するためには、高い化学的均一・性と、易焼成性を
有する組成物材料を必要と４゛る。そのためにはＰＬＺ
Ｔの原料粉末は、湿式法により調製Ｃることか望ましい
ときれている。ｌ？ＩＩ式法ではＰＬＺＴを得る方法は
、これまでいくつか提案されている。しかし、構成陽イ
オンのうらでＰｂ１イオンが定ＩＡ的に沈殿し難いため
、組成の正確な制御は困難であった。[Prior art] PLZT of a system in which La is added to Pb(Zr, Ti)O.
can be made into a transparent sintered body, and the electro-optic conversion element t
It is used as. In order to prepare such a PLZT crystal, a composition material having high chemical uniformity and property and easy sinterability is required. For that purpose, PLZ
It is preferable that the raw material powder of T is prepared by a wet method. l? Several methods have been proposed so far for obtaining PLZT using the II method. However, since Pb1 ions are difficult to precipitate behind the constituent cations in a constant IA manner, it has been difficult to accurately control the composition.
［発明が解決しようとする問題点］
本発明で技術的に解決するための課題は、化学的に均一
で、焼成したときに容易に焼結できるＰＬＺＴ材料を調
製でき、その材料を焼成することにより、ＰＬＺＴを合
成する方法を提供することである。即ち、本発明は、Ｐ
ｂ”、Ｌ ａ ＆ ＋、Ｚｒ４°、Ｔ ｉ ”などのＰ
ＬＺＴを構成する元素を均一に配して、焼結され易い沈
殿物を得、それを焼結し、容易に結晶化ＰＬＺＴを得る
方法を提供することを目的にする。[Problems to be Solved by the Invention] The problems to be technically solved by the present invention are to be able to prepare a PLZT material that is chemically uniform and easily sintered when fired, and to sinter the material. Accordingly, an object of the present invention is to provide a method for synthesizing PLZT. That is, the present invention provides P
b", L a & +, Zr4°, T i ", etc.
The object of the present invention is to provide a method of uniformly distributing elements constituting LZT to obtain a precipitate that is easily sintered, and sintering the precipitate to easily obtain crystallized PLZT.
［発明の構成］
［問題点を解決するための手段］
本発明は、上記の技術的な課題の解決のために、ツルー
１ニウム塩溶液とチタニウム塩溶液を混合し、アン［ニ
ア溶液を添加し、沈殿物を得て、更にその沈殿物を硝酸
で溶解し、必要により、希り類元素を添加し、更に、酸
化鉛を添加溶解した溶液に、キレート剤を添加し、ｐＨ
を調整しながら沈殿物を得、洗浄濾過し、乾燥して得た
所望組成のＰＬＺＴ組成物を焼成することよりＰＬＺＴ
を合成する方法を提供する。この場合、このキレート剤
は、オキシンであり、調整ｐＨの範囲は、８〜１２．３
の範囲であることが好適である。また、前記所望組成の
ＰＬＺＴキレート沈殿物を、焼成前に、減圧下で昇温す
ることによりキレート化合物を昇華きせる工程を更に含
むことが好適である。また、キレート剤がオキシンであ
る場合に、調整ｐＨの範囲は、８．４〜８．６がより好
適である。[Structure of the Invention] [Means for Solving the Problems] In order to solve the above-mentioned technical problem, the present invention mixes a true 1 nium salt solution and a titanium salt solution, and adds an un[near solution]. Then, obtain a precipitate, dissolve the precipitate in nitric acid, add rare elements if necessary, add lead oxide, add a chelating agent to the dissolved solution, and adjust the pH.
A precipitate is obtained while adjusting the PLZT composition, which is then washed, filtered, and dried to obtain a PLZT composition.
Provides a method for synthesizing. In this case, the chelating agent is oxine and the adjusted pH range is 8-12.3.
It is preferable that the range is within the range of . Further, it is preferable to further include a step of sublimating the chelate compound by heating the PLZT chelate precipitate having the desired composition under reduced pressure before firing. Further, when the chelating agent is oxine, the adjusted pH range is more preferably 8.4 to 8.6.
本発明は、有機キレート試薬が、種々のイオンを定理的
に沈殿させ得ることに着目し、有機キレート試薬を用い
て、ＰＬＺＴを合成する方法を見出したものである。The present invention focuses on the fact that organic chelating reagents can theoretically precipitate various ions, and has discovered a method for synthesizing PLZT using organic chelating reagents.
即ち、ＰＬＺＴの構成イオンは、Ｐｂ”、Ｌａ５０、Ｚ
ｒ”、Ｔ ｉ ”テあり、コｔｔうを４″ヘテ沈殿さ
せ得るキレート試薬を用いて、化学的に均一な沈殿物を
得る方法を見出し、この知見に基づいて本発明を為した
ものである。That is, the constituent ions of PLZT are Pb'', La50, Z
We have discovered a method to obtain a chemically uniform precipitate using a chelating reagent that can precipitate 4" and T i ", and based on this knowledge, we have created the present invention. be.
このためキレート試薬として、オキシンが最も好適であ
ることを見出した。即ち、ＰＬＺＴを構成するイオンで
あるｐｂ”、Ｌ ａ”、Ｚ ｒ ４ ＊、ＴＭｅをすべ
て沈殿させ得るキレート試薬として、オキシンを用いる
。これらＰｂ”、Ｌ ａ ＊ ４、Ｚｒ０、Ｔ ｉ ”
イオンを溶解させた溶液に、オキシンを溶解し、各イオ
ンのオキシン塩の溶解度以上の濃度を作る溶解オキシン
量にする必要がある。然し乍ら、オキシンの溶解度は非
常に低く、必要と４°るオキシン盪以−Ｆを溶解するこ
とは、実際−ヒ困難である。そこで溶解度以−］二の量
のオキシンを用いて、未溶解のオキシンが存在している
状態で操作を行なうことが好適である。このように常に
オキシンの飽和状態を保持するようにする。然し乍ら、
市販のオキシン粉末は、溶解速度が遅いため沈殿物形成
に消費される猜を速やかに補充することができないこと
を見出した。そこでオキシンを微結晶にすることにより
、その溶解速度を実質上大きく４゛ることかできる、−
とを見出した。For this reason, we have found that oxine is the most suitable chelating reagent. That is, oxine is used as a chelating reagent that can precipitate all of the ions constituting PLZT, pb", L a ", Z r 4 *, and TMe. These Pb", L a * 4, Zr0, T i "
It is necessary to dissolve oxine in a solution in which ions are dissolved, and to make the amount of dissolved oxine such that the concentration is higher than the solubility of each ion's oxine salt. However, the solubility of oxine is very low, and it is actually difficult to dissolve the required 4 degrees of oxine. Therefore, it is preferable to use an amount of oxine equal to or higher than the solubility and to carry out the operation in the presence of undissolved oxine. In this way, the oxine saturation state is always maintained. However,
It has been found that commercially available oxine powders cannot rapidly replenish the water consumed in precipitate formation due to their slow dissolution rates. Therefore, by making oxine into microcrystals, its dissolution rate can be substantially increased by 4 degrees.
I discovered that.
即ら、キレート試薬を、所望のイオンを含有する溶液に
溶解し、必要とする量の溶解キレート試薬が溶液中に供
給されるようにするために、例えば、キレート試薬を塩
酸又は硝酸に溶解し、アンモニアにより必要なｐＨ範囲
に調整し、微細な結晶のキレート試薬を析出させ、この
析出キレート試薬微結晶を含む溶液を用いて、上記のＰ
ｂ”、Ｌａ１、Ｚ ｒ”、Ｔ ｉ ”″イオンのキレー
ト塩を形成せしめる。即ち、この微結晶キレート試薬沈
殿物は、溶解速度が大きく、キレート試薬の溶解度の低
い点は解決された。That is, the chelating reagent is dissolved in a solution containing the desired ions and the required amount of dissolved chelating reagent is provided in the solution, for example, by dissolving the chelating reagent in hydrochloric acid or nitric acid. , adjust the pH to the required range with ammonia, precipitate the chelating reagent in the form of fine crystals, and use the solution containing the precipitated chelating reagent microcrystals.
chelate salts of ions such as ``b'', La1, Z r'', and T i '''' are formed. That is, this microcrystalline chelating reagent precipitate had a high dissolution rate, and the problem of low solubility of the chelating reagent was solved.
このキレート試薬としてオキシンを用いた場合、Ｐｂ”
、Ｌａ１、Ｚｒ”、Ｔ ４４′″の各オキシン塩として
、沈殿させるｐＨｖａ囲は、各々、８゜４〜１２．３．
６．５〜１０．３．４．７〜１２．５及び４．８〜８．
６であるため、この全ＰＬＺＴ構成成分をオキシン塩と
して同時に沈殿させるｐＨｆａ囲は、上記の各ｐＨ範囲
の全部の重複範囲であるｐＨ−８，４〜８．６の範囲で
ある。When oxine is used as this chelating reagent, Pb”
, La1, Zr", and T44'", the precipitated pHva range is 8°4 to 12.3.
6.5-10.3.4.7-12.5 and 4.8-8.
6, the pH range in which all the PLZT components are simultaneously precipitated as oxine salts is in the range of pH-8.4 to 8.6, which is the overlapping range of each of the above pH ranges.
また、Ｔ ｉ ＩＩ、 Ｌ ａＩＩ、Ｚ ｒ”イオンに
ついては、水〜塩として沈殿できるために、−１−記Ｔ
ｉ ”によるｐＨ範囲の上限ｐＨ−８，６等による沈
殿物形成限界は、考慮する必要はなく、Ｐｂ”のオキシ
ン塩の形成するｐＨ範囲たるｐＨ−８，４〜１２．３の
みを考慮して、調整ｐＨ範囲を決めることができる。In addition, T i II, La II, Z r" ions can be precipitated from water to salt, so T
There is no need to consider the precipitate formation limit due to the upper limit of the pH range due to Pb'', such as pH -8.6, and only the pH range of pH -8.4 to 12.3, which is the pH range in which the oxine salt of Pb'' is formed, is considered. The adjustment pH range can be determined by
以上の点を考慮して、調整ｐＨｍ囲は、８〜１２．３と
した。即ち、ｐＨが８以下では、Ｐｂ”″イオンのオキ
シン塩の形成が不十分で、化学的均一性が不十分である
。また、ｐＨが１２．３以上でＰｂ１＋イオンの塩の形
成が不十分となり、化学的均一性が不十分となる。Considering the above points, the adjusted pH range was set to 8 to 12.3. That is, when the pH is lower than 8, the formation of oxine salt of Pb"" ions is insufficient, resulting in insufficient chemical uniformity. Furthermore, if the pH is 12.3 or higher, the formation of salts of Pb1+ ions becomes insufficient, resulting in insufficient chemical uniformity.
このｐＨ範囲に溶解液を保持するために、アンモニア−
塩化アンモニウム系又はアンモニア−硝酸アンモニウム
の緩衝液を用いることが好適である。以１−のように各
ＰＬＺＴ構成成分を含有”する溶液から、化学的均一性
を有するキレート塩及び／水酸塩の沈殿物を得る。To maintain the solution in this pH range, ammonia
It is preferred to use ammonium chloride-based or ammonia-ammonium nitrate buffers. As described in 1- below, a chemically homogeneous chelate salt and/or hydroxide precipitate is obtained from a solution containing each PLZT component.
尚、各金属イオンのオキシン塩の沈殿を生成させる際に
、金属イオン溶液の滴下に伴ってｐＨ値が酸性側にずれ
る傾向があるので、アンモニア水添加によりｐＨ値の調
整を行ないながら、金属イオン溶液の滴下を行なう必要
がある。In addition, when forming a precipitate of oxine salts of each metal ion, the pH value tends to shift to the acidic side as the metal ion solution is added dropwise, so while adjusting the pH value by adding aqueous ammonia, the metal ion It is necessary to drip the solution.
次に、この得られた沈殿物をよく清浄し、過剰のキレー
ト試薬を取り除いた。然し乍ら、過剰のキレート試薬を
完全に沈殿物から洗浄除去することは困難である。その
ために、次の沈殿物の乾燥工程中に、残留していたキレ
ート試薬の融解が見られた。即ち、沈殿物の乾燥中に、
過剰のオキシンが融解し、沈殿物中の化学的均一性を損
なう危険があると考えられる。これを避けるために、本
発明においては、得られた沈殿物を減圧下に加熱昇温し
、過剰のオキシン或いはキレート試薬を昇やさせて、除
いた。The resulting precipitate was then thoroughly cleaned to remove excess chelating reagent. However, it is difficult to completely wash away excess chelating reagent from the precipitate. Therefore, during the subsequent drying step of the precipitate, melting of the remaining chelating reagent was observed. That is, during drying of the precipitate,
It is believed that there is a risk that excess oxine will melt and impair chemical homogeneity in the precipitate. In order to avoid this, in the present invention, the obtained precipitate is heated to an elevated temperature under reduced pressure to raise and remove excess oxine or chelating reagent.
即ら、得られた沈殿物を洗浄しなければならないが、過
剰に含有されたキレート試薬を完全に洗浄することは困
難であるに加えて、沈殿物を乾燥４−る工程において、
残留したキレート試薬が、融解することがあり、そのた
めに、沈殿物中の各イオン等の化学的均一性を損なう原
因となると考えられ、残留キレ−１・試薬はできるだけ
避けなければならない、そこで、本発明の合成方法では
、減圧下で沈殿物を昇温し、キレート試薬を昇華させる
ことにより沈殿物中の残留キレート試薬量を削減或いは
０になるようにする。That is, the obtained precipitate must be washed, but it is difficult to completely wash away the excessively contained chelating reagent, and in addition, in the step of drying the precipitate,
The residual chelate reagent may melt, which is considered to be the cause of impairing the chemical uniformity of each ion in the precipitate, and the residual chelate reagent must be avoided as much as possible. In the synthesis method of the present invention, the temperature of the precipitate is raised under reduced pressure and the chelating reagent is sublimated, thereby reducing or eliminating the amount of the chelating reagent remaining in the precipitate.
次いで、キレート化合物の熱分解を図った。然し乍ら、
直接高温で熱分解を行なうと、キレート化合物自体が融
解することがあり、これも化学的均一性を損なう原因と
なる危険がある。このキレート化合物の融解を避けつつ
、熱分解するために沈殿物の昇温速度に注意しつつ昇温
する必要がある。この熱分解を行なうことにより、ペロ
ブスカイト型結晶構造のＰＬＺＴが生成できる。Next, thermal decomposition of the chelate compound was attempted. However,
Direct thermal decomposition at high temperatures may cause the chelate compound itself to melt, which also poses a risk of impairing chemical uniformity. In order to thermally decompose the chelate compound while avoiding melting, it is necessary to raise the temperature while paying attention to the heating rate of the precipitate. By performing this thermal decomposition, PLZT having a perovskite crystal structure can be produced.
以上の本発明によるＰＬＺＴの合成方法を、第１図のフ
【１−シートに示す。The above method for synthesizing PLZT according to the present invention is shown in FIG.
即ら、フローシートに示すように、ＺｒＯＣｌｍの水溶
液とＴｉＣｊ！を水溶液を調製し、所望のモル比になる
ような割合で混合し、次に、アンモニア水添加し、ジル
；１ニウム及びチタンの水酸塩の沈殿さける０次に、塩
素イオンを沈殿物より除去するために、よく水で洗浄し
、塩素イオンのない水酸塩沈殿物を得る６次に、この水
酸塩沈殿物を硝酸で溶解し、硝酸溶液にする。更に、こ
の硝酸溶液に、酸化鉛と酸化ランタンを所望量添加する
。That is, as shown in the flow sheet, an aqueous solution of ZrOClm and TiCj! An aqueous solution is prepared and mixed at a desired molar ratio, and then aqueous ammonia is added to prevent precipitation of dillium and titanium hydroxides.Next, chloride ions are removed from the precipitate. In order to remove it, it is thoroughly washed with water to obtain a hydroxide precipitate free of chloride ions.6 Next, the hydroxide precipitate is dissolved in nitric acid to form a nitric acid solution. Furthermore, desired amounts of lead oxide and lanthanum oxide are added to this nitric acid solution.
一方、キレート試薬であるオキシンを希塩酸又は硝酸に
溶解し、更にそのオキシン溶解塩機又は硝酸溶液に、ア
ンモニア水を添加し、ｐＨを８゜４〜８，６の範囲に調
整しながら、約５８°Ｃに加温すると、アルカリ性によ
りオキシンが沈殿し、微結晶のオキシンを含有するアル
カリ性溶液が得られる。この微結晶オキシン沈殿を有す
る溶液に、前記のように調製した所望モル比でＰＬＺＴ
構成金属を溶解させた溶液を添加する。同時に、添加溶
液が酸性であるために、アンモニア水を添加しながら、
混合溶液のｐＨを８．４〜８．６の範囲に調整すると、
加温溶液から、各金属のオキシン塩を所望モル比で含有
４−る沈殿物が生成する。On the other hand, oxine, which is a chelating reagent, is dissolved in dilute hydrochloric acid or nitric acid, and aqueous ammonia is added to the oxine dissolving salt machine or nitric acid solution, and the pH is adjusted to a range of 8.4 to 8.6. When heated to 0.degree. C., oxine precipitates due to alkalinity, yielding an alkaline solution containing microcrystalline oxine. To this solution containing the microcrystalline oxine precipitate was added PLZT at the desired molar ratio prepared as described above.
Add a solution in which the constituent metals are dissolved. At the same time, since the addition solution is acidic, while adding ammonia water,
When the pH of the mixed solution is adjusted to a range of 8.4 to 8.6,
A precipitate containing the desired molar ratio of oxine salts of each metal is formed from the heated solution.
得られた沈殿物を洗浄濾過し、十分に蒸留水で洗浄し、
過剰のオキシンを取り除く。The resulting precipitate was washed and filtered, thoroughly washed with distilled water,
Removes excess oxine.
この沈殿物を加熱し、焼成膚゛ると容易にＰＬＺＴ原料
粉末を調製できる。By heating this precipitate and firing it, a PLZT raw material powder can be easily prepared.
本発明によるＰＬＺＴの合成づｊ法は、ＰＬＺＴ合成だ
けでなく、多種の金属イオンを含有するセシミックス材
料の調製にも適用できることが期待される。It is expected that the PLZT synthesis method according to the present invention can be applied not only to PLZT synthesis but also to the preparation of seshimix materials containing various metal ions.
次に本発明によるＰＬＺＴ合成方法を具体的に実施例に
より説明するが、本発明はそれらによって限定されるも
のではない。Next, the method for synthesizing PLZT according to the present invention will be specifically explained using Examples, but the present invention is not limited thereto.
［実施例］
第１図のフ１１−シートに従って、Ｚ ｒ ＯＣｌ ｍ
水溶液と、Ｔ ｉ Ｃｌ ｍ水溶液を所望のＺｒ：Ｔｉ
のモル比率により、混合し、アンモニア水を添加し、沈
殿物を形成し、濾過、洗浄し、得られた沈殿物をＨＮＯ
，に溶解し、Ｌ ａ ｒ ＯＩも所望モル比添加溶解し
、更にＰｂＯを溶解して、Ｐｂ”、Ｌａ″４、ｚｒ′４
、Ｔ ｉ ”を所望モル比で含有する溶液を得た。[Example] According to the sheet 11 of FIG. 1, Z r OCl m
aqueous solution and T i Cl m aqueous solution to desired Zr:Ti
Mix, add aqueous ammonia, form a precipitate, filter and wash the resulting precipitate with HNO
, L a r OI is added and dissolved in the desired molar ratio, and PbO is further dissolved to form Pb'', La''4, zr'4.
, T i ” in the desired molar ratio was obtained.
一方、１キシンを希塩醜に溶解し、アンモニアによりｐ
Ｈ８，４〜８．６の範囲に調整した溶液を作成した。こ
の溶液を前記のように作成したＰｂ１、Ｌａ１、ｚ「４
′″、Ｔｉ”を所望モル比で含有した溶液と、アンモニ
ア水を添加しながら、混合した。アンモニア水は混合溶
液全体のＩ）Ｈが、８．４〜８．６になるように添加す
るものである。すると、溶液から各イオンのオキシン塩
が沈殿した。得られた沈殿物を濾過し、よく洗浄した後
、乾燥した。On the other hand, 1xine was dissolved in dilute salt and purified with ammonia.
A solution adjusted to a range of H8.4 to 8.6 was prepared. This solution was mixed with Pb1, La1, z'4 prepared as described above.
``'' and Ti'' in a desired molar ratio were mixed with a solution containing ammonia water while adding aqueous ammonia. Aqueous ammonia is added so that I)H of the entire mixed solution is 8.4 to 8.6. Then, oxine salts of each ion precipitated from the solution. The resulting precipitate was filtered, thoroughly washed, and then dried.
この沈殿物を減圧下で加熱し、過剰のオキシンを昇華し
、取り除いた０次に、得られた沈殿物を第２図の昇温パ
ターンで昇温しながら、Ｘａ回折による観察で、反応を
見、生成される反応物を観察した結果を、同じ第２図に
示す、生成物によるＸ線回折強度で、示すために、生成
物の生成喰を示すものではないが、おおよそのＩＪ安が
得られた。This precipitate was heated under reduced pressure to sublimate and remove excess oxine. The reaction was observed by Xa diffraction while heating the resulting precipitate according to the temperature increase pattern shown in Figure 2. The results of observing the reactants produced are shown in the X-ray diffraction intensity of the product shown in Figure 2. Although it does not indicate the amount of product produced, the approximate IJ value is shown in Figure 2. Obtained.
即ち、２２５°Ｃまでは、０．１４°Ｃ／時間の速度で
昇温し、２２５℃に１０時間保持し、次に３２０１０ま
で０．１４℃／時間の昇温速度で昇温し、３２０℃で５
時間保持した。３２０℃からは、８°Ｃ／時間の急速な
昇温速度で５００°Ｃまで昇温した。これに対して、第
２図に示されるように、先ず、有機金属Ａのｘ６回折線
が見られ、次に、１８０°Ｃ付近から有機金属ＢのＸ線
回折線が見られ、３２０°Ｃ付近からｐｔ、ｚｒノＸ、
１１１回折線とＰｂｏのＸ線回折線が見られ、ＰＬＺＴ
結晶が２３０°Ｃ付近から生成されたことを示す、そし
て、３２０°Ｃ以上でＰＬＺＴ結晶によるＸ線回折線の
強度が急速に増加している。That is, the temperature was raised at a rate of 0.14°C/hour to 225°C, held at 225°C for 10 hours, then the temperature was raised to 32010 at a rate of 0.14°C/hour, and the temperature was increased to 320°C. 5 at °C
Holds time. From 320°C, the temperature was increased to 500°C at a rapid temperature increase rate of 8°C/hour. On the other hand, as shown in Figure 2, first, the x6 diffraction line of organometallic A is seen, then the X-ray diffraction line of organometallic B is seen from around 180°C, and then at 320°C. From nearby pt, zr no x,
The 111 diffraction line and the Pbo X-ray diffraction line are seen, and PLZT
This indicates that the crystals were formed from around 230°C, and the intensity of the X-ray diffraction line due to the PLZT crystal increases rapidly above 320°C.
この昇温加熱でより、金属オキシン塩が熱分解した後の
粉末を化学分析し、出発溶液の成分比と比較した。出発
溶液と、粉末との成分比が一致していることが判った０
本発明によるＰＬＺＴ合成法では、構成金属イ〕ンを全
て定敬的沈殿きせることができたことが示された。The powder after the metal oxine salt was thermally decomposed by heating was chemically analyzed and compared with the component ratio of the starting solution. It was found that the component ratios of the starting solution and powder were the same.
It was shown that the PLZT synthesis method according to the present invention was able to regularly precipitate all the constituent metal ions.
以上により得られたＰ Ｌ Ｚ’Ｔの構成金属イオンの
Ａキシン塩による沈殿物は、３２０℃焼成で結晶化し、
ぺ「１シス力イト型化合物になった。これに対し、湿式
法で作成された沈殿物は、５５０℃付近で結晶化すると
いう報告があるが、本発明いよる合成法では、それより
も２３０℃も低温で結晶化したことになる０本発明によ
るＰＬＺＴの原料粉末は、非常に反応性がよいことが分
かった。The precipitate of the Axin salt of the constituent metal ions of P L Z'T obtained above is crystallized by calcination at 320°C,
On the other hand, there are reports that the precipitate created by the wet method crystallizes at around 550°C, but the synthesis method of the present invention has a higher temperature than that. It was found that the raw material powder of PLZT according to the present invention, which was crystallized at a low temperature of 230° C., had very good reactivity.
以−Ｆによって得られたＰＬＺＴ原料粉末を、１２００
°Ｃで本焼成した後に、Ｘ線回折線で観察した結果Ａと
、乾式法で得られるＰＬＺＴ原料粉末による結果Ｂと比
較した。その結果を、第３図に示１０本発明により合成
されるＰＬＺＴは結晶が微細であることを示している。The PLZT raw material powder obtained by above-F was heated to 1200
After main firing at °C, results A observed by X-ray diffraction were compared with results B obtained from PLZT raw material powder obtained by a dry method. The results are shown in FIG. 3, which shows that PLZT synthesized according to the present invention has fine crystals.
［発明の効果］
本発明のＰＬＺＴ合成方法は、以上のようなことにより
、以下のような種々の顕著な技術的効果が得られた。[Effects of the Invention] As described above, the PLZT synthesis method of the present invention has achieved various remarkable technical effects as described below.
第１に、化学的均一性が高いＰＬＺＴ原料粉末が得られ
、そのために、すぐれた特性の透明焼結体ＰＬＺＴが得
られ安い。First, a PLZT raw material powder with high chemical uniformity can be obtained, and therefore a transparent sintered PLZT body with excellent properties can be obtained at a low cost.
第２に、本発明により得られたＰＬＺＴＭ料粉末は、従
来の湿式法で得られるものと比べて、非常に焼結性が高
く、そのために、著しい低温でも焼成焼成でき、結晶が
得られる。Second, the PLZTM material powder obtained by the present invention has extremely high sintering properties compared to those obtained by conventional wet methods, and therefore can be fired even at extremely low temperatures to obtain crystals.
第３に、ＰＬＺＴを構成する金属イオンが、所望モル比
にあるＰＬＺＴ結晶を、容易に得られるＰＬＺＴ合成法
が提供できる。Thirdly, it is possible to provide a PLZT synthesis method that easily produces a PLZT crystal in which the metal ions constituting PLZT have a desired molar ratio.
第１図は、本発明によるＰＬＺＴ合成法をフローレート
で示すものである。
第２図は、本発明により調製された沈殿物を加熱焼成し
た場合の、加熱パターンと生成きれたものをＸ線回折線
による観察の結果を示す。
第３図は、本発明により調製された試料と乾式法で調製
された試料とを、１２００℃での本焼成での結果得られ
たもののＸ線回折線で、比較Ｃるものである。
特許出願人 住友セメント株式会社
代理人 弁理上 倉 持 裕
ζ洗浄・濾か乾燥
第１図FIG. 1 shows the PLZT synthesis method according to the present invention in terms of flow rate. FIG. 2 shows the heating pattern and the results of observation of the formed product by X-ray diffraction when the precipitate prepared according to the present invention was heated and calcined. FIG. 3 compares a sample prepared according to the present invention and a sample prepared by a dry method using X-ray diffraction lines obtained as a result of main firing at 1200°C. Patent applicant Sumitomo Cement Co., Ltd. Agent Hiroshi Kuramochi ζ Washing and filtering drying Figure 1
Claims (4)
、アンモニア溶液を添加し、沈殿物を得て、更にその沈
殿物を硝酸で溶解し、必要により、希土類元素を添加し
、更に、酸化鉛を添加溶解した溶液と、キレート剤と混
合し、ｐＨを調整しながら沈殿物を得、洗浄濾過し、乾
燥して得た所望組成のＰＬＺＴ組成物を焼成することを
特徴とするＰＬＺＴの合成方法。(1) Mix zirconium salt solution and titanium salt solution, add ammonia solution to obtain a precipitate, further dissolve the precipitate with nitric acid, add rare earth elements if necessary, and add lead oxide. A method for synthesizing PLZT, which comprises mixing the added and dissolved solution with a chelating agent, obtaining a precipitate while adjusting the pH, washing and filtering, and drying the resulting PLZT composition having a desired composition.
範囲は、８〜１２．３の範囲である特許請求の範囲第１
項記載のＰＬＺＴの合成方法。(2) The chelating agent is oxine, and the adjusted pH range is from 8 to 12.3.
Method for synthesizing PLZT as described in section.
前に、減圧下で昇温することによりキレート化合物を昇
華させることを更にに含むことを特徴とする特許請求の
範囲第２項記載のＰＬＺＴの合成方法。(3) The PLZT according to claim 2, further comprising sublimating the chelate compound by heating the PLZT chelate precipitate having the desired composition under reduced pressure before firing. synthesis method.
である特許請求の範囲第２項のＰＬＺＴの合成方法。(4) The method for synthesizing PLZT according to claim 2, wherein the adjusted pH range is from 8.4 to 8.6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63125835A JP2647436B2 (en) | 1988-05-25 | 1988-05-25 | PLZT synthesis method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63125835A JP2647436B2 (en) | 1988-05-25 | 1988-05-25 | PLZT synthesis method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01298023A true JPH01298023A (en) | 1989-12-01 |
| JP2647436B2 JP2647436B2 (en) | 1997-08-27 |
Family
ID=14920115
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63125835A Expired - Lifetime JP2647436B2 (en) | 1988-05-25 | 1988-05-25 | PLZT synthesis method |
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| Country | Link |
|---|---|
| JP (1) | JP2647436B2 (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50116399A (en) * | 1974-02-22 | 1975-09-11 | ||
| JPS6140819A (en) * | 1984-08-01 | 1986-02-27 | Denki Kagaku Kogyo Kk | Manufacture of lead titanate and zirconate |
| JPS61106457A (en) * | 1984-10-30 | 1986-05-24 | 科学技術庁無機材質研究所長 | Manufacturing method of PLZT translucent ceramics |
| JPS61275165A (en) * | 1985-05-27 | 1986-12-05 | 株式会社村田製作所 | Manufacture of light permeable ceramics |
-
1988
- 1988-05-25 JP JP63125835A patent/JP2647436B2/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50116399A (en) * | 1974-02-22 | 1975-09-11 | ||
| JPS6140819A (en) * | 1984-08-01 | 1986-02-27 | Denki Kagaku Kogyo Kk | Manufacture of lead titanate and zirconate |
| JPS61106457A (en) * | 1984-10-30 | 1986-05-24 | 科学技術庁無機材質研究所長 | Manufacturing method of PLZT translucent ceramics |
| JPS61275165A (en) * | 1985-05-27 | 1986-12-05 | 株式会社村田製作所 | Manufacture of light permeable ceramics |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2647436B2 (en) | 1997-08-27 |
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