CN1583667A - Preparation of zirconium barium titanate with inorganic zirconium as source - Google Patents
Preparation of zirconium barium titanate with inorganic zirconium as source Download PDFInfo
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- CN1583667A CN1583667A CN 200410043616 CN200410043616A CN1583667A CN 1583667 A CN1583667 A CN 1583667A CN 200410043616 CN200410043616 CN 200410043616 CN 200410043616 A CN200410043616 A CN 200410043616A CN 1583667 A CN1583667 A CN 1583667A
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- hexylene glycol
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- zirconium
- citric acid
- tetrabutyl titanate
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Abstract
A process for preparing the sol of barium zirconate titanate from inorganic zirconium includes such steps as dissolving zirconium nitrate oxide in deionized water, adding citric acid to odtain zirconium citrate, dissolving it in hexanediol to obtain solution A, dissolving tetrabutyl titanate in hexanediol to obtain solution B, mixing the solution of barium acetate in acitic acid with solution B to obtain solution C, mixing solution A with solution C, and stirring.
Description
Technical field:
The present invention relates to the preparation technology of inorganic materials, is the technology that the zirconium source prepares zirconium barium titanate colloidal sol with inorganic zirconium particularly.
Background technology:
Stupalith becomes the important branch in material field undisputedly, is more and more paid attention in scientific research and Application Areas, and the research of ceramic material and application become a dazzling field undoubtedly.It has been widely used in leading-edge fields such as space technology, ocean exploitation, electronic technology, information technology, automatic control.Preparing high-performance, high quality, highly purified stupalith is the quality and the bottleneck of performance of material.Therefore, it is very crucial how preparing such stupalith.In recent years, the develop rapidly of electronic product, computer, information products, advancing by leaps and bounds of domestic air mail space industry research all required the raising as the performance of basi components, and therefore research and the application as the electronic devices and components of basi components presents the prosperous flourishing scene of a slice.The research of multi-layer capacitor and the prosperity scene of application just are being based on such background.Barium titanate crystal powder Ba of the same clan (Zr
xTi
1-x) O
3Have excellent dielectric properties, promoted laminated ceramic capacitor (MLCC) to realize above many optimization in Properties and raising.Prepare form accurately, purity crystal powder high, spherical, narrow particle size distribution is the key that reaches this target.At present, electrical condenser adopts solid reaction process synthetic with the zirconium barium titanate powder more, owing to mix inhomogeneous in the solid state reaction, reaction interface is big, the chemical constitution tolerance range is low, and is beneficial to that dielectric properties improve and mostly adulterated trace element is to introduce the solid phase additive, simultaneously cause the active low etc. all multifactor of powder, bring many factors of instability to the production of electrical condenser because calcined temperature is too high.On the other hand, in recent years, because high performance piezoelectric is widely used in piezoelectric ceramic transformer, PZT (piezoelectric transducer) etc., people were more and more high for the concern of high tension performance material.Although lead is family's material, especially Pb-based lanthanumdoped zirconate titanates (PZT) shows huge potential in this regard, and plumbous volatility is brought harm to environment significantly, and people seek the ceramic systems that can replace Pb-based lanthanumdoped zirconate titanates, Ba (ZrTi) O constantly
3Ceramic systems is undoubtedly noticeable candidate.Ba (ZrTi) O
3Pottery has showed that along with the content difference of zirconium different phases changes, and modification Ba (ZrTi) O
3Also be accompanied by the change of system and change with aspect of performance such as transformation mutually in dielectric properties, piezoelectric property.When being in paraelectric state, the BZT film can well be as stochastic and dynamic storer and adjustable dielectric equipment when being higher than Curie temperature.Because plumbous volatility make plumbous system be difficult to make high-quality relaxation oscillation device film, and the BZT film has very big chance to achieve success in this respect.Shanghai silicate institute discloses in CN1350071A a kind of " the wet chemistry method technology of preparing of unleaded zirconium barium titanate function ceramics film ", this method is to be the zirconium source with the propyl alcohol zirconium, the easy hydrolysis of propyl alcohol zirconium, not only waste resource (can not use again after the hydrolysis), and give to synthesize and bring many inconvenience, of paramount importance is to be difficult to industrialization; Be difficult to buy, cost an arm and a leg; And used the only methyl ether of hexylene glycol, hexanoyl acetone and other organic solvent, this solvent has certain toxicity, contaminate environment, and increased the technology cost.
Summary of the invention:
The purpose of this invention is to provide a kind of high purity, low cost, free of contamination be the method that the zirconium source prepares zirconium barium titanate colloidal sol with inorganic zirconium, this zirconium barium titanate colloidal sol can further be processed into zirconium barium titanate ceramics powder and zirconium barium titanate film.Zirconium barium titanate colloidal sol of the present invention is achieved in that a, Zircosol ZN is dissolved in the deionized water, stir, treat to add citric acid again after Zircosol ZN dissolves fully, wherein the weight ratio of Zircosol ZN and citric acid is 2: (4～6), stir to clarify clear solution, regulate pH=3～4 with ammoniacal liquor, obtain the citric acid zirconium solution, the citric acid zirconium is dissolved in the hexylene glycol, wherein the mol ratio of citric acid zirconium and hexylene glycol is 1: (8～12), at 100～120 ℃ of following constant temperature 0.5～1h, obtain the hexylene glycol solution of citric acid zirconium in the placement thermostatic drying chamber; B, barium acetate is dissolved in the acetic acid solution that is made into barium acetate in the acetate under the condition of 50～70 ℃ of constant temperature, wherein the weight ratio of barium acetate and acetate is 1: (1～3) is cooled to room temperature; C, tetrabutyl titanate is dissolved in the hexylene glycol solution that is made into tetrabutyl titanate in the hexylene glycol, wherein the weight ratio of tetrabutyl titanate and hexylene glycol is 1: (1～3); D, the acetic acid solution of barium acetate and the hexylene glycol solution of tetrabutyl titanate are mixed; E, the hexylene glycol solution of the citric acid zirconium that anhydrates is moved in the mixed system of barium acetate and tetrabutyl titanate, wherein the volume ratio of the hexylene glycol solution of the acetic acid solution of the hexylene glycol solution of citric acid zirconium, barium acetate and tetrabutyl titanate is 1: (3～5): (2～4); F, above-mentioned mixed solution is stirred 0.5～1h under 30～50 ℃ temperature, obtain BZT colloidal sol.Sol-gel method of the present invention has been realized the mixing of molecular level, can prepare further that chemical constitution is accurate, purity is high, good uniformity, sphere, narrow particle size distribution (40～60nm), BZT crystal powder that reactive behavior is high, and provide the presoma of premium propertiess such as stable, appropriate viscosity for film technique; Zirconium titanium ratio can accurately be controlled; Adopting inorganic zirconium is the zirconium source, and acetate and hexylene glycol at a low price is solvent, and Zircosol ZN among the present invention and citric acid are as easy as rolling off a log having bought, and cheap; Do not need to use deleterious organic solvents such as the only methyl ether of hexylene glycol, hexanoyl acetone, further reduced cost (cost than CN1350071A reduces more than 2 times); Adopting inorganic zirconium is the zirconium source, has removed the problem of the as easy as rolling off a log hydrolysis of organic zirconium from, and not there is such problem in the complexing body of Zircosol ZN and citric acid zirconium, thereby is that realization industrialization, saving resource have been created advantageous conditions; Unleaded in the system, there is not problem of environmental pollution, be environmentally friendly material; The colloidal sol homogeneous that makes, stable can be placed standby for a long time.The present invention has that cost is low, purity is high, save energy, free of contamination advantage.
Embodiment:
Embodiment one: the zirconium barium titanate colloidal sol of present embodiment is achieved in that a, Zircosol ZN is dissolved in the deionized water, stir, treat to add citric acid again after Zircosol ZN dissolves fully, wherein the weight ratio of Zircosol ZN and citric acid is 2: (4～6), stir to clarify clear solution, regulate pH=3～4 with ammoniacal liquor, obtain the citric acid zirconium solution, the citric acid zirconium is dissolved in the hexylene glycol, wherein the mol ratio of citric acid zirconium and hexylene glycol is 1: (8～12), at 100～120 ℃ of following constant temperature 0.5～1h, obtain the hexylene glycol solution of citric acid zirconium in the placement thermostatic drying chamber; B, barium acetate is dissolved in the acetic acid solution that is made into barium acetate in the acetate under the condition of 50～70 ℃ of constant temperature, wherein the weight ratio of barium acetate and acetate is 1: (1～3) is cooled to room temperature; C, tetrabutyl titanate is dissolved in the hexylene glycol solution that is made into tetrabutyl titanate in the hexylene glycol, wherein the weight ratio of tetrabutyl titanate and hexylene glycol is 1: (1～2); D, the acetic acid solution of barium acetate and the hexylene glycol solution of tetrabutyl titanate are mixed; E, the hexylene glycol solution of the citric acid zirconium that anhydrates is moved in the mixed system of barium acetate and tetrabutyl titanate, wherein the volume ratio of the hexylene glycol solution of the acetic acid solution of the hexylene glycol solution of citric acid zirconium, barium acetate and tetrabutyl titanate is 1: (3～5): (2～4); F, above-mentioned mixed solution is stirred 0.5～1h under 30～50 ℃ temperature, obtain zirconium barium titanate (BZT) colloidal sol.
Embodiment two: the zirconium barium titanate colloidal sol of present embodiment is achieved in that a, Zircosol ZN is dissolved in the deionized water, stir, treat to add citric acid again after Zircosol ZN dissolves fully, wherein the weight ratio of Zircosol ZN and citric acid is 2: 5, stir to clarify clear solution, regulate pH=3.5 with ammoniacal liquor, obtain the citric acid zirconium solution, the citric acid zirconium is dissolved in the hexylene glycol, wherein the mol ratio of citric acid zirconium and hexylene glycol is 1: 10, at 100～120 ℃ of following constant temperature 0.5～1h, obtain the hexylene glycol solution of citric acid zirconium in the placement thermostatic drying chamber; B, barium acetate is dissolved in the acetic acid solution that is made into barium acetate in the acetate under the condition of 60 ℃ of constant temperature, wherein the weight ratio of barium acetate and acetate is 1: 2, is cooled to room temperature; C, tetrabutyl titanate is dissolved in the hexylene glycol solution that is made into tetrabutyl titanate in the hexylene glycol, wherein the weight ratio of tetrabutyl titanate and hexylene glycol is 1: 1.5; D, the acetic acid solution of barium acetate and the hexylene glycol solution of tetrabutyl titanate are mixed; E, the hexylene glycol solution of the citric acid zirconium that anhydrates is moved in the mixed system of barium acetate and tetrabutyl titanate, wherein the volume ratio of the hexylene glycol solution of the acetic acid solution of the hexylene glycol solution of citric acid zirconium, barium acetate and tetrabutyl titanate is 1: 4: 3; F, above-mentioned mixed solution is stirred 1h under 40 ℃ temperature, obtain BZT colloidal sol.Adopt technology of the present invention to synthesize 0.015molBa (Zr
0.2Ti
0.8) O
3Cost be 3.05 yuan, and be 8.75 yuan with the cost of the product of the synthetic same weight of pure zirconium, cost of the present invention has almost reduced by 2/3rds.
Embodiment three: the barium titanate colloidal sol of present embodiment can be used as the presoma of barium titanate ceramic powder, its barium titanate ceramic powder is achieved in that a, the Zircosol ZN of weighing 0.04mol dissolves in the deionized water of 68ml, magnetic stirrer is dissolved fully, the citric acid that adds 0.12mol, continue to stir until being clear solution, regulate pH=3.5 with ammoniacal liquor, the citric acid zirconium is dissolved in the hexylene glycol, wherein the mol ratio of citric acid zirconium and hexylene glycol is 1: 10, at 100～120 ℃ of following constant temperature 0.5～1h, obtain the hexylene glycol solution of citric acid zirconium in the placement thermostatic drying chamber; B, barium acetate is dissolved in the acetic acid solution that is made into barium acetate in the acetate under the condition of 60 ℃ of constant temperature, wherein the weight ratio of barium acetate and acetate is 1: 2, is cooled to room temperature; C, tetrabutyl titanate is dissolved in the hexylene glycol solution that is made into tetrabutyl titanate in the hexylene glycol, wherein the weight ratio of tetrabutyl titanate and hexylene glycol is 1: 1.5; D, the acetic acid solution of barium acetate and the hexylene glycol solution of tetrabutyl titanate are mixed; E, the hexylene glycol solution of the citric acid zirconium that anhydrates is moved in the mixed system of barium acetate and tetrabutyl titanate, wherein the volume ratio of the hexylene glycol solution of the acetic acid solution of the hexylene glycol solution of citric acid zirconium, barium acetate and tetrabutyl titanate is 1: 4: 3; F, above-mentioned mixed solution is stirred 1h under 40 ℃ temperature, obtain BZT colloidal sol; G, this sol system is placed in thermostatic drying chamber at 100～120 ℃ of following constant temperature 48～72h, obtained BZT gel crystal grain; H, gel crystal grain ground after, 800 ℃ of following calcining pretreatment, obtain.This powder is by XRD, SEM, TEM test, and the result shows that the BZT ceramic powder is that homogeneous thing phase, sphere distribute, particle diameter is 40～60nm.
Embodiment four: the barium titanate colloidal sol of present embodiment can be used as the presoma of barium titanate film, its barium titanate film is achieved in that a, the Zircosol ZN of weighing 0.04mol dissolves in the deionized water of 68ml, magnetic stirrer is dissolved fully, the citric acid that adds 0.12mol, continue to stir until being clear solution, regulate pH=3.5 with ammoniacal liquor, the citric acid zirconium is dissolved in the hexylene glycol, wherein the mol ratio of citric acid zirconium and hexylene glycol is 1: 10, at 100～120 ℃ of following constant temperature 0.5～1h, obtain the hexylene glycol solution of citric acid zirconium in the placement thermostatic drying chamber; B, barium acetate is dissolved in the acetic acid solution that is made into barium acetate in the acetate under the condition of 60 ℃ of constant temperature, wherein the weight ratio of barium acetate and acetate is 1: 2, is cooled to room temperature; C, tetrabutyl titanate is dissolved in the hexylene glycol solution that is made into tetrabutyl titanate in the hexylene glycol, wherein the weight ratio of tetrabutyl titanate and hexylene glycol is 1: 1.5; D, the acetic acid solution of barium acetate and the hexylene glycol solution of tetrabutyl titanate are mixed; E, the hexylene glycol solution of the citric acid zirconium that anhydrates is moved in the mixed system of barium acetate and tetrabutyl titanate, wherein the volume ratio of the hexylene glycol solution of the acetic acid solution of the hexylene glycol solution of citric acid zirconium, barium acetate and tetrabutyl titanate is 1: 4: 3; F, above-mentioned mixed solution is stirred 1h under 40 ℃ temperature, obtain BZT colloidal sol; G, BZT colloidal sol is dropped on the silicon substrate, utilize sol evenning machine to drive substrate and carry out equal glue, form " wet film " with the rotating speed of 3000～5000r/min; H, the wet film that will obtain carry out wet film thermal treatment under 700～900 ℃ temperature, form the BZT film.
Claims (2)
1, with inorganic zirconium is the method that the zirconium source prepares zirconium barium titanate colloidal sol, it is characterized in that it is achieved in that a, Zircosol ZN is dissolved in the deionized water, stir, treat to add citric acid again after Zircosol ZN dissolves fully, wherein the weight ratio of Zircosol ZN and citric acid is 2: (4～6), stir to clarify clear solution, regulate pH=3～4 with ammoniacal liquor, obtain the citric acid zirconium solution, the citric acid zirconium is dissolved in the hexylene glycol, wherein the mol ratio of citric acid zirconium and hexylene glycol is 1: (8～12) at 100～120 ℃ of following constant temperature 0.5～1h, obtain the hexylene glycol solution of citric acid zirconium in the placement thermostatic drying chamber; B, barium acetate is dissolved in the acetic acid solution that is made into barium acetate in the acetate under the condition of 50～70 ℃ of constant temperature, wherein the weight ratio of barium acetate and acetate is 1: (1～3) is cooled to room temperature; C, tetrabutyl titanate is dissolved in the hexylene glycol solution that is made into tetrabutyl titanate in the hexylene glycol, wherein the weight ratio of tetrabutyl titanate and hexylene glycol is 1: (1～2); D, the acetic acid solution of barium acetate and the hexylene glycol solution of tetrabutyl titanate are mixed; E, the hexylene glycol solution of the citric acid zirconium that anhydrates is moved in the mixed system of barium acetate and tetrabutyl titanate, wherein the volume ratio of the hexylene glycol solution of the acetic acid solution of the hexylene glycol solution of citric acid zirconium, barium acetate and tetrabutyl titanate is 1: (3～5): (2～4); F, above-mentioned mixed solution is stirred 0.5～1h under 30～50 ℃ temperature, obtain BZT colloidal sol.
2, according to claim 1 is the method that the zirconium source prepares zirconium barium titanate colloidal sol with inorganic zirconium, it is characterized in that it is achieved in that a, Zircosol ZN is dissolved in the deionized water, stir, treat to add citric acid again after Zircosol ZN dissolves fully, wherein the weight ratio of Zircosol ZN and citric acid is 2: 5, stir to clarify clear solution, regulate pH=3.5 with ammoniacal liquor, obtain the citric acid zirconium solution, the citric acid zirconium is dissolved in the hexylene glycol, wherein the mol ratio of citric acid zirconium and hexylene glycol is 1: 10, at 100～120 ℃ of following constant temperature 0.5～1h, obtains the hexylene glycol solution of citric acid zirconium in the placement thermostatic drying chamber; B, barium acetate is dissolved in the acetic acid solution that is made into barium acetate in the acetate under the condition of 60 ℃ of constant temperature, wherein the weight ratio of barium acetate and acetate is 1: 2, is cooled to room temperature; C, tetrabutyl titanate is dissolved in the hexylene glycol solution that is made into tetrabutyl titanate in the hexylene glycol, wherein the weight ratio of tetrabutyl titanate and hexylene glycol is 1: 1.5; D, the acetic acid solution of barium acetate and the hexylene glycol solution of tetrabutyl titanate are mixed; E, the hexylene glycol solution of the citric acid zirconium that anhydrates is moved in the mixed system of barium acetate and tetrabutyl titanate, wherein the volume ratio of the hexylene glycol solution of the acetic acid solution of the hexylene glycol solution of citric acid zirconium, barium acetate and tetrabutyl titanate is 1: 4: 3; F, above-mentioned mixed solution is stirred 1h under 40 ℃ temperature, obtain BZT colloidal sol.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100402435C (en) * | 2005-12-20 | 2008-07-16 | 湘潭大学 | Process for preparing barium titanate nano-rod |
| CN101104562B (en) * | 2007-06-04 | 2011-12-21 | 仙桃市中星电子材料有限公司 | Constant pressure hydro-thermal preparation method for barium zirconate titanate powder |
| CN106986634A (en) * | 2017-04-28 | 2017-07-28 | 信阳师范学院 | A kind of calcium barium zirconate titanate base piezoceramics and preparation method thereof |
| CN109516804A (en) * | 2019-01-09 | 2019-03-26 | 兰州大学 | A kind of preparation method of leadless piezoelectric ceramics that widening high performance operation temperature range |
-
2004
- 2004-06-09 CN CN 200410043616 patent/CN1232475C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100402435C (en) * | 2005-12-20 | 2008-07-16 | 湘潭大学 | Process for preparing barium titanate nano-rod |
| CN101104562B (en) * | 2007-06-04 | 2011-12-21 | 仙桃市中星电子材料有限公司 | Constant pressure hydro-thermal preparation method for barium zirconate titanate powder |
| CN106986634A (en) * | 2017-04-28 | 2017-07-28 | 信阳师范学院 | A kind of calcium barium zirconate titanate base piezoceramics and preparation method thereof |
| CN109516804A (en) * | 2019-01-09 | 2019-03-26 | 兰州大学 | A kind of preparation method of leadless piezoelectric ceramics that widening high performance operation temperature range |
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| CN1232475C (en) | 2005-12-21 |
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