CN100337979C - Method for preparing perovskite phase lead zirconate titanate powder - Google Patents

Method for preparing perovskite phase lead zirconate titanate powder Download PDF

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CN100337979C
CN100337979C CNB200510062153XA CN200510062153A CN100337979C CN 100337979 C CN100337979 C CN 100337979C CN B200510062153X A CNB200510062153X A CN B200510062153XA CN 200510062153 A CN200510062153 A CN 200510062153A CN 100337979 C CN100337979 C CN 100337979C
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powder
zirconium
zirconate titanate
lead zirconate
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CN1803711A (en
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韩高荣
徐刚
任召辉
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Zhejiang University ZJU
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Abstract

The present invention relates to a method for preparing perovskite phase lead zirconate titanate powder, which adopts a two-step deposition to realize the preparation of the precursor powder of synthetic lead zirconate titanate. Firstly, tetrabutyl titanate and zirconium oxychloride are used as raw materials, anhydrous alcohol and deionized water are used as solvent, ammonia water is used as precipitant, and zirconate titanate oxyhydroxide is prepared by coprecipitation. After being washed in deionized water, the prepared precipitate is dispersed to ammonia water solution; then lead nitrate solution is introduced to the ammonia water solution for precipitating Pb<2+> ions, and the precursor powder of synthetic lead zirconate titanate is obtained by filtering, washing with deionized water, dewatering with anhydrous alcohol and drying. The precursor powder of synthetic lead zirconate titanate is calcined to obtain pure perovskite phase lead zirconate titanate powder. Compared with a solid reaction method and a coprecipitation method, the present invention has the advantages of no generation of intermediate phases, high purity of the synthetic powder, high stability, convenient source of raw materials, low cost, simple and convenient operation, high adaptability, little environment pollution, and easy realization of industrial large-scale production.

Description

The preparation method of perovskite phase lead zirconate titanate powder
Technical field
The present invention relates to a kind of preparation method of perovskite phase lead zirconate titanate powder, belong to field of functional materials.
Background technology
Pb-based lanthanumdoped zirconate titanates (PbZr xTi 1-xO 3, PZT) be the 1950's Shirane and his co-worker at first invent, remain research up to now and use maximum ferroelectric materials.With other piezoelectric ceramics compare, the PZT pottery not only has high Curie temperature (about 380 ℃) and piezo-electric modulus (about 600pm/V), and be easy to doping vario-property, has stability preferably, thereby have very important status in the electric mechanical production, be the base mateiral of most of electro-mechanical devices such as preparation sonar, nautical receiving set, ultra-sonic generator, high volt generator and fine position device.
At present, the method for industrial synthetic uhligite phase PZT powder mainly still is traditional solid reaction process.But, the intermediate reaction of lead titanate (PT) or lead zirconates (ZT) often takes place to form in the calcination process of the synthetic PZT powder of solid reaction process, cause in final product, existing a little P T or PZ phase; And often containing a large amount of hard agglomerations in the prepared powder of solid reaction process, sintering activity is low, need be easy to produce the PbO volatilization at higher sintering temperature; Cause prepared PZT stupalith to contain second mutually and depart from chemical constitution, performance reduces.Although coprecipitation method is a kind of effective ways of synthesizing inorganic oxide powder, but when utilizing this method to synthesize the PZT powder, because Pb aggregation of particles, except that generating principal crystalline phase PZT, also have small amounts of Pb O to form mutually, cause institute's synthetic powder thermostability relatively poor, be difficult to prepare the PZT pottery of excellent performance.
Summary of the invention
The object of the present invention is to provide the preparation method that a kind of technological process is simple, be easy to suitability for industrialized production, perovskite phase lead zirconate titanate (PZT) powder that purity is high.
The perovskite phase lead zirconate titanate powder of the present invention's preparation, its chemical formula is: PbZr xTi 1-xO 3, 0≤x≤1.0.
The preparation method may further comprise the steps:
(1) by the chemical formula PbZr that desires the synthetic PZT powder xTi 1-xO 3, 0≤x≤1.0, weighing tetrabutyl titanate and zirconium oxychloride are dissolved in respectively in dehydrated alcohol and the deionized water solvent, and compound concentration is that tetrabutyl titanate ethanol solution and the concentration of 0.05～0.25M/L is the zirconium oxychloride aqueous solution of 0.05～0.30M/L;
(2) under whipped state, the tetrabutyl titanate ethanol solution is joined in the zirconium oxychloride aqueous solution, obtain zirconium, titanium ion mixing solutions, with concentration of metal ions to the 0.05～0.25M/L in the deionized water regulator solution;
(3) under whipped state, zirconium, titanium ion mixing solutions are added drop-wise in the ammonia soln that concentration is 0.10～0.30M/L, leave standstill, sedimentation, filtration, washed with de-ionized water, obtain zirconium, the co-precipitation of titanium oxyhydroxide;
(4) with zirconium, titanium oxyhydroxide co-precipitation mechanical dispersion in the ammonia soln of concentration 0.1～0.3M/L, obtain being suspended with the ammonia soln of zirconium, the co-precipitation of titanium oxyhydroxide;
(5) by the chemical formula weighing lead nitrate of desiring the synthetic PZT powder, be dissolved in deionized water, compound concentration is the solution of 0.05～0.20M/L lead nitrate;
(6) under the state that stirs, lead nitrate solution is dripped in the ammonia soln that contains zirconium, the co-precipitation of titanium oxyhydroxide, leave standstill, sedimentation, filtration, washed with de-ionized water, dehydrated alcohol dehydration, oven dry, obtain the presoma powder of synthetic PZT powder;
(7) the presoma powder is calcined in 400～900 ℃ of scopes, obtained the pure perovskite phase lead zirconate titanate powder.
Among the present invention, the purity of used tetrabutyl titanate, zirconium oxychloride, lead nitrate and dehydrated alcohol and ammoniacal liquor all is not less than chemical pure.
The present invention has strengthened zirconium, the combination of titanium ion in the presoma powder that occupy same structural junction, and suppressed the gathering of lead ion in the reaction process, overcome the shortcoming of solid reaction process and coprecipitation method, prevented the formation of intermediate phase lead titanate, lead zirconates and plumbous oxide phase, synthetic PZT powder is a pure perovskite phase powder, and have good thermostability, help the PZT stupalith of processability excellence.Technological process of the present invention is simple, and easy handling is pollution-free, the PZT powder purity height of preparing, and cost is low, is easy to commercial scale production.
Description of drawings
Fig. 1 is synthetic perovskite phase lead zirconate titanate PbZr of the present invention 0.52Ti 0.48O 3The XRD figure spectrum of powder;
Fig. 2 is synthetic perovskite phase lead zirconate titanate PbZr of the present invention 0.4Ti 0.6O 3The XRD figure spectrum of powder;
Fig. 3 is synthetic perovskite phase lead zirconate titanate PbZr of the present invention 0.6Ti 0.4O 3The XRD figure spectrum of powder.
Embodiment
Further specify the present invention below in conjunction with embodiment.
Example 1
By the synthetic pure perovskite phase PbZr of following processing step 0.52Ti 0.48O 3Powder.
(1) take by weighing tetrabutyl titanate by chemical dosage ratio and zirconium oxychloride is dissolved in respectively in dehydrated alcohol and the deionized water solvent, compound concentration is the tetrabutyl titanate ethanol solution of 0.08M/L and the zirconium oxychloride aqueous solution of 0.15M/L;
(2) under the state of Jiao Baning, the tetrabutyl titanate ethanol solution is added drop-wise in the zirconyl chloride solution, obtains containing Zr 4+, Ti 4+The mixing solutions of two metal ion species is 0.10M/L with the concentration of metal ions in the deionized water regulator solution;
(3) will contain Zr 4+, Ti 4+The mixing solutions of two metal ion species is added drop-wise in the ammonia soln of 0.15M/L and generates metal hydroxy oxide compound co-precipitation zirconium, two kinds of ions of titanium under the state that stirs.Leave standstill, sedimentation, filter, with washed with de-ionized water 6 times, obtain zirconium, the co-precipitation of titanium oxyhydroxide;
(4) zirconium, the co-precipitation of titanium oxyhydroxide with preparation utilizes mechanical stirring, and brute force is scattered in the ammonia soln, and obtaining ammonia concn is the ammonia soln that is suspended with the co-precipitation of zirconium titanium oxyhydroxide of 0.15M/L;
(5) by stoichiometric ratio weighing lead nitrate, be dissolved in the deionized water solvent, obtain the lead nitrate solution that concentration is 0.10M/L;
(6) under the state that stirs, lead nitrate solution is added drop-wise to generation lead hydroxide precipitation lead ion in the ammonia soln that contains the co-precipitation of zirconium titanium oxyhydroxide.Leave standstill, sedimentation, filter, with washed with de-ionized water 6 times, dehydrated alcohol cleaning and dewatering 2 times, oven dry, obtain the presoma powder of synthetic PZT powder;
(7) the presoma powder of preparation was calcined 3 hours synthetic PZT powder at 500 ℃.Detect through XRD, institute's synthetic powder is pure perovskite phase PbZr 0.52Ti 0.48O 3The powder (see figure 1).
Example 2
By the synthetic pure perovskite phase PbZr of following processing step 0.40Ti 0.60O 3Powder.
(1) take by weighing tetrabutyl titanate by chemical dosage ratio and zirconium oxychloride is dissolved in respectively in dehydrated alcohol and the deionized water solvent, compound concentration is the tetrabutyl titanate ethanol solution of 0.05M/L and the zirconium oxychloride aqueous solution of 0.20M/L;
(2) under the state of Jiao Baning, the tetrabutyl titanate ethanol solution is added drop-wise in the zirconyl chloride solution, obtains containing Zr 4+, Ti 4+The mixing solutions of two metal ion species is 0.10M/L with the concentration of metal ions in the deionized water regulator solution;
(3) will contain Zr 4+, Ti 4+The mixing solutions of two metal ion species is added drop-wise in the ammonia soln of 0.10M/L and generates zirconium, titanium two metal ion species oxyhydroxide co-precipitation under the state that stirs.Leave standstill, sedimentation, filter, with washed with de-ionized water 6 times, obtain zirconium, the co-precipitation of titanium oxyhydroxide.
(4) zirconium, the co-precipitation of titanium oxyhydroxide with preparation utilizes mechanical stirring, and brute force is scattered in the ammonia soln, and obtaining ammonia concn is the ammonia soln that is suspended with the co-precipitation of zirconium titanium oxyhydroxide of 0.15M/L;
(5) by stoichiometric ratio weighing lead nitrate, be dissolved in the deionized water solvent, obtain the lead nitrate solution that concentration is 0.05M/L;
(6) under the state that stirs, lead nitrate solution is added drop-wise to generation lead hydroxide precipitation lead ion in the ammonia soln that contains the co-precipitation of zirconium titanium oxyhydroxide.Leave standstill, sedimentation, filter, with washed with de-ionized water 6 times, dehydrated alcohol cleaning and dewatering 2 times, oven dry, obtain the presoma powder of synthetic PZT powder;
(7) the presoma powder of preparation was calcined 3 hours synthetic PZT powder at 700 ℃.Detect through XRD, institute's synthetic powder is pure perovskite phase PbZr 0.40Ti 0.60O 3The powder (see figure 2).
Example 3
By the synthetic pure perovskite phase PbZr of following processing step 0.60Ti 0.40O 3Powder.
(1) take by weighing tetrabutyl titanate by chemical dosage ratio and zirconium oxychloride is dissolved in respectively in dehydrated alcohol and the deionized water solvent, compound concentration is the tetrabutyl titanate ethanol solution of 0.15M/L and the zirconium oxychloride aqueous solution of 0.10M/L;
(2) under the state that stirs, the tetrabutyl titanate ethanol solution is added drop-wise in the zirconyl chloride solution, obtains containing Zr 4+, Ti 4+The mixing solutions of two metal ion species is 0.10M/L with the concentration of metal ions in the deionized water regulator solution;
(3) will contain Zr 4+, Ti 4+The mixing solutions of two metal ion species is added drop-wise in the ammonia soln of 0.2M/L and generates metal hydroxy oxide compound co-precipitation zirconium, two kinds of ions of titanium under the state that stirs.Leave standstill, sedimentation, filter, with washed with de-ionized water 6 times, obtain zirconium, the co-precipitation of titanium oxyhydroxide.
(4) zirconium, the co-precipitation of titanium oxyhydroxide with preparation utilizes mechanical stirring, and brute force is scattered in the ammonia soln, and obtaining ammonia concn is the ammonia soln that is suspended with the co-precipitation of zirconium titanium oxyhydroxide of 0.15M/L;
(5) by stoichiometric ratio weighing lead nitrate, be dissolved in the deionized water solvent, obtain the lead nitrate solution that concentration is 0.12M/L;
(6) under the state that stirs, lead nitrate solution is added drop-wise to generation lead hydroxide precipitation lead ion in the ammonia soln that contains the co-precipitation of zirconium titanium oxyhydroxide.Leave standstill, sedimentation, filter, with washed with de-ionized water 6 times, dehydrated alcohol cleaning and dewatering 2 times, oven dry, obtain the presoma powder of synthetic PZT powder;
(7) the presoma powder of preparation was calcined 3 hours synthetic PZT powder at 900 ℃.Detect through XRD, institute's synthetic powder is pure perovskite phase PbZr 0.60Ti 0.40O 3The powder (see figure 3).

Claims (2)

1. the preparation method of perovskite phase lead zirconate titanate powder is characterized in that may further comprise the steps:
(1) by the chemical formula PbZr that desires the synthetic PZT powder xTi 1-xO 3, 0≤x≤1.0, weighing tetrabutyl titanate and zirconium oxychloride are dissolved in respectively in dehydrated alcohol and the deionized water solvent, and compound concentration is that tetrabutyl titanate ethanol solution and the concentration of 0.05～0.25M/L is the zirconium oxychloride aqueous solution of 0.05～0.30M/L;
(2) under whipped state, the tetrabutyl titanate ethanol solution is joined in the zirconium oxychloride aqueous solution, obtain zirconium, titanium ion mixing solutions, with concentration of metal ions to the 0.05～0.25M/L in the deionized water regulator solution;
(3) under whipped state, zirconium, titanium ion mixing solutions are added drop-wise in the ammonia soln that concentration is 0.10～0.30M/L, leave standstill, sedimentation, filtration, washed with de-ionized water, obtain zirconium, the co-precipitation of titanium oxyhydroxide;
(4) with zirconium, titanium oxyhydroxide co-precipitation mechanical dispersion in the ammonia soln of concentration 0.1～0.3M/L, obtain being suspended with the ammonia soln of zirconium, the co-precipitation of titanium oxyhydroxide;
(5) by the chemical formula weighing lead nitrate of desiring the synthetic PZT powder, be dissolved in deionized water, compound concentration is the solution of 0.05～0.20M/L lead nitrate;
(6) under the state that stirs, lead nitrate solution is dripped in the ammonia soln that contains zirconium, the co-precipitation of titanium oxyhydroxide, leave standstill, sedimentation, filtration, washed with de-ionized water, dehydrated alcohol dehydration, oven dry, obtain the presoma powder of synthetic PZT powder;
(7) the presoma powder is calcined in 400～900 ℃ of scopes, obtained the pure perovskite phase lead zirconate titanate powder.
2. the preparation method of perovskite phase lead zirconate titanate powder according to claim 1 is characterized in that the purity of said tetrabutyl titanate, zirconium oxychloride, lead nitrate and dehydrated alcohol and ammoniacal liquor all is not less than chemical pure.
CNB200510062153XA 2005-12-21 2005-12-21 Method for preparing perovskite phase lead zirconate titanate powder Expired - Fee Related CN100337979C (en)

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CN101550014B (en) * 2009-05-12 2012-08-08 聊城大学 Preparation method of lead based relaxor ferroelectric ceramic powder material with pure perovskite structure

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Publication number Priority date Publication date Assignee Title
CN1267654A (en) * 2000-04-06 2000-09-27 中国科学院上海技术物理研究所 Preparation of ferroelectric lead zirconate titanate film material
US6395080B1 (en) * 1989-08-28 2002-05-28 Richard B. Cass Refractory filaments
US6592805B1 (en) * 1998-06-11 2003-07-15 National University Of Singapore Method for producing sintered electroceramic materials from hydroxide and oxalate precursors
CN1623664A (en) * 2003-12-03 2005-06-08 浙江大学 Titanium zirconium Sosoloid and preparation process thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6395080B1 (en) * 1989-08-28 2002-05-28 Richard B. Cass Refractory filaments
US6592805B1 (en) * 1998-06-11 2003-07-15 National University Of Singapore Method for producing sintered electroceramic materials from hydroxide and oxalate precursors
CN1267654A (en) * 2000-04-06 2000-09-27 中国科学院上海技术物理研究所 Preparation of ferroelectric lead zirconate titanate film material
CN1623664A (en) * 2003-12-03 2005-06-08 浙江大学 Titanium zirconium Sosoloid and preparation process thereof

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
Pb(Zr0.53Ti0.47)O3陶瓷超细粉体制备及分散研究 胡志强，中国陶瓷工业，第11卷第6期 2004 *
共沉淀法制备富锆PZT粉体及其烧结特性的研究 郭丽，无机材料学报，第17卷第6期 2002 *
部分草酸铅法共沉淀合成Pb(Zr0.52Ti0.42)O3(PZT)粉体 徐刚，材料科学与工程学报，第23卷第4期 2005 *
锆钛酸铅纳米陶瓷粉体的水热合成技术 李涛，中国粉体技术，第4期 2004 *
锆钛酸铅陶瓷的烧结研究进展 王军霞，陶瓷，第6期 2004 *

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