CN102887705A - Preparation method of tetragonal-phase barium titanate (BaTiO3) hollow nanocrystal - Google Patents
Preparation method of tetragonal-phase barium titanate (BaTiO3) hollow nanocrystal Download PDFInfo
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Abstract
The invention discloses a preparation method of a tetragonal-phase barium titanate (BaTiO3) hollow nanocrystal. The preparation method comprises the following steps of: using barium acetate and tetrabutyl titanate as raw materials, adding deionized water, adding potassium hydroxide of an appropriate amount to promote crystallization, and carrying out hydrothermal reaction at the temperature of 110-240 DEG C so as to prepare the tetragonal-phase barium titanate (BaTiO3) hollow nanocrystal. The preparation method is simple in technical process, easy in control, low in cost and easy in scale production. The prepared product is high in purity, good in crystallinity, good in dispersivity and narrow in particle size distribution. The product has wide application prospects in the fields of microelectronic devices, high-capacity capacitors, sensors, storage materials, piezoelectric ceramics, filters and the like.
Description
Technical field
The present invention relates to the nanocrystalline preparation method of a kind of tetragonal-phase barium titanate hollow, belong to field of inorganic nonmetallic material.
Background technology
The performance of functional materials depends on their pattern, size and degree of crystallinity to a great extent, and the control of microscopic appearance has very large value to the utilization of material.Nano material has the physicochemical property more excellent than block materials, and the progress of science and technology and the miniaturization of electron device, and the nanometer of material has also been proposed increasing requirement.Therefore, the preparation of control appearance of nano material becomes the focus of in recent years Materials science concern and research.
Barium titanate BaTiO
3A kind of widely used ferroelectric, piezoceramic material, mainly for the production of the electronic devices and components such as ceramic condenser of high dielectric.In recent years along with the development of laminated ceramic capacitor, to BaTiO
3The performance requriements of powder improves, and demand increases.Facts have proved, realize BaTiO
3High-purity, even, nanometer be to improve BaTiO
3One of effective measure of electronic component performance.
The method that tradition prepares tetragonal-phase barium titanate mainly adopts high temperature solid-state method, but the powder granule of preparation is thick, surfactivity is poor, reunion is serious, form segregation, and the size of particle and pattern also are difficult to control, finally can greatly affect the electrical property of electronic devices and components.Hydrothermal method is a kind of evenly controlled material preparation method, has the advantages such as environmental protection, power consumption be low, easy to control, is commonly used to prepare the product of various multicomponent systems, also be a kind of nano material preparation method commonly used, and this method is simple to operate, and is low for equipment requirements, with low cost.
Summary of the invention
The object of the present invention is to provide a kind of technique simply to prepare barium titanate BaTiO
3Nanocrystalline method.
Barium titanate BaTiO of the present invention
3Nanocrystalline preparation method may further comprise the steps:
1) in tetrabutyl titanate, adds deionized water, sequestrant and hydrolysis inhibitor, normal pressure and 50-80 ℃ of lower the stirring 4-24 hour, the pH value of control reactant is 2-3, obtain the water-soluble colloidal sol of titaniferous, the mol ratio of tetrabutyl titanate, deionized water, sequestrant and hydrolysis inhibitor is 1:150 ~ 300:0.1 ~ 0.6:0.01 ~ 0.04, described sequestrant is the one or both combination in quadrol and the methyl ethyl diketone, and hydrolysis inhibitor is the one or both combination in hydrochloric acid and the nitric acid.
2) take by weighing barium acetate by barium acetate and tetrabutyl titanate mol ratio 3:1 metering, barium acetate is added in the deionized water, fully stir, form the aqueous solution of barium acetate;
3) potassium hydroxide being dissolved in deionized water, with step 2) aqueous solution of the barium acetate that makes joins potassium hydroxide aqueous solution, joins in the water-soluble colloidal sol of titaniferous of step 1) again, obtains containing the suspension of the oxyhydroxide precipitation of barium and titanium;
The suspension that 4) will contain the oxyhydroxide precipitation of barium and titanium is transferred in the reactor inner bag, reach the 70%-90% of reactor inner bag volume with the reaction mass volume in the deionized water conditioned reaction still inner bag, stirred at least 10 minutes, in the reaction mass, the volumetric molar concentration of barium acetate is 0.375 mol/L, the volumetric molar concentration of tetrabutyl titanate is 0.125mol/L, and the volumetric molar concentration of potassium hydroxide is 2 ~ 4 mol/L, and the volume radix of volumetric molar concentration is the volume of material in all introducing reactor inner bags;
5) the reactor inner bag that step 4) is disposed reaction mass places reactor, sealing, carried out hydrothermal treatment consists in 6-24 hour 120 ℃-240 ℃ lower insulations, then allow reactor naturally cool to room temperature, with deionized water and dehydrated alcohol repetitive scrubbing reaction product, filter, dry, obtain tetragonal-phase barium titanate BaTiO
3Hollow is nanocrystalline.
In the preparation process of the present invention, the reactor that uses is polytetrafluoroethylliner liner, the reactor that the stainless steel external member is airtight.
Among the present invention, the purity of said barium acetate, tetrabutyl titanate, potassium hydroxide, quadrol, methyl ethyl diketone and dehydrated alcohol all is not less than chemical pure.
The tetragonal-phase barium titanate BaTiO that the inventive method makes
3Nanocrystalline size is 20-100 nm.
Beneficial effect of the present invention is:
The present invention adopts simple solvent-thermal method to prepare purity height, good crystallinity, good dispersity, the narrow nanometer tetra phase barium titanate powder of size distribution.Technological process of the present invention is simple, and processing condition are easy to control, and cost is low, is easy to large-scale production.The cubic phase nano barium carbonate powder that the present invention makes is having broad application prospects in fields such as microelectronic device, high capacity capacitor, sensor, storage medium, piezoelectric ceramics, wave filters.
Description of drawings
Fig. 1 is the XRD figure spectrum of the bismuth ferrite monocrystalline micron film for preparing of the present invention;
Fig. 2 is the stereoscan photograph of the bismuth ferrite monocrystalline micron film for preparing of the present invention;
Embodiment
Further specify the present invention below in conjunction with embodiment.
Example 1
1) in tetrabutyl titanate, adds deionized water, quadrol and hydrochloric acid, the mol ratio of tetrabutyl titanate, deionized water, quadrol and hydrochloric acid is that 1:260:0.3:0.03 is normal pressure and 80 ℃ of lower stirrings 6 hours, the pH value of control reactant is 2, obtains the water-soluble colloidal sol of titaniferous.
2) take by weighing barium acetate by barium acetate and tetrabutyl titanate mol ratio 3:1 metering, barium acetate is added in the deionized water, fully stir, form the aqueous solution of barium acetate;
3) potassium hydroxide being dissolved in deionized water, with step 2) aqueous solution of the barium acetate that makes joins potassium hydroxide aqueous solution, joins in the water-soluble colloidal sol of titaniferous of step 1) again, obtains containing the suspension of the oxyhydroxide precipitation of barium and titanium;
The suspension that 4) will contain the oxyhydroxide precipitation of barium and titanium is transferred in the reactor inner bag, reach 90% of reactor inner bag volume with the reaction mass volume in the deionized water conditioned reaction still inner bag, stirred 10 minutes, in the reaction mass, the volumetric molar concentration of barium acetate is 0.375 mol/L, the volumetric molar concentration of tetrabutyl titanate is 0.125mol/L, and the volumetric molar concentration of potassium hydroxide is 4 mol/L, and the volume radix of volumetric molar concentration is the volume of material in all introducing reactor inner bags;
5) the reactor inner bag that step 4) is disposed reaction mass places reactor, sealing, carried out hydrothermal treatment consists in 12 hours 160 ℃ of lower insulations, then allow reactor naturally cool to room temperature, with deionized water and dehydrated alcohol repetitive scrubbing reaction product, filter, dry, obtain tetragonal-phase barium titanate BaTiO
3Hollow is nanocrystalline, and size is 20-100 nm.
Example 2
1) add deionized water, methyl ethyl diketone and nitric acid in tetrabutyl titanate, the mol ratio of tetrabutyl titanate, deionized water, methyl ethyl diketone and nitric acid is 1:280:0.37:0.04.Normal pressure and 60 ℃ of lower stirrings 10 hours, the pH value of control reactant is 3, obtains the water-soluble colloidal sol of titaniferous.
2) take by weighing barium acetate by barium acetate and tetrabutyl titanate mol ratio 3:1 metering, barium acetate is added in the deionized water, fully stir, form the aqueous solution of barium acetate;
3) potassium hydroxide being dissolved in deionized water, with step 2) aqueous solution of the barium acetate that makes joins potassium hydroxide aqueous solution, joins in the water-soluble colloidal sol of titaniferous of step 1) again, obtains containing the suspension of the oxyhydroxide precipitation of barium and titanium;
The suspension of the oxyhydroxide precipitation that contains barium and titanium that 4) will obtain is transferred in the reactor inner bag, reach 80% of reactor inner bag volume with the reaction mass volume in the deionized water conditioned reaction still inner bag, stirred 10 minutes, in the reaction mass, the volumetric molar concentration of barium acetate is 0.375 mol/L, the volumetric molar concentration of tetrabutyl titanate is 0.125mol/L, and the volumetric molar concentration of potassium hydroxide is 4 mol/L, and the volume radix of volumetric molar concentration is the volume of material in all introducing reactor inner bags;
5) the reactor inner bag that step 4) is disposed reaction mass places reactor, sealing, carried out hydrothermal treatment consists in 6 hours 200 ℃ of lower insulations, then allow reactor naturally cool to room temperature, with deionized water and dehydrated alcohol repetitive scrubbing reaction product, filter, dry, obtain tetragonal-phase barium titanate BaTiO
3Hollow is nanocrystalline, and its XRD figure spectrum is seen Fig. 1, as seen from the figure high, the good crystallinity of its purity; Scanning electron microscope (SEM) photo is seen Fig. 2.Tetragonal-phase barium titanate BaTiO
3The nanocrystalline size of hollow is 20-100 nm.
Example 3
1) add deionized water, methyl ethyl diketone and hydrochloric acid in tetrabutyl titanate, the mol ratio of tetrabutyl titanate, deionized water, methyl ethyl diketone and hydrochloric acid is 1:210:0.45:0.01.Normal pressure and 50 ℃ of lower stirrings 24 hours, the pH value of control reactant is 3, obtains the water-soluble colloidal sol of titaniferous.
2) take by weighing barium acetate by barium acetate and tetrabutyl titanate mol ratio 3:1 metering, barium acetate is added in the deionized water, fully stir, form the aqueous solution of barium acetate;
3) potassium hydroxide being dissolved in deionized water, with step 2) aqueous solution of the barium acetate that makes joins potassium hydroxide aqueous solution, joins in the water-soluble colloidal sol of titaniferous of step 1) again, obtains containing the suspension of the oxyhydroxide precipitation of barium and titanium;
The suspension of the oxyhydroxide precipitation that contains barium and titanium that 4) will obtain is transferred in the reactor inner bag, reach 70% of reactor inner bag volume with the reaction mass volume in the deionized water conditioned reaction still inner bag, stirred 10 minutes, in the reaction mass, the volumetric molar concentration of barium acetate is 0.375 mol/L, the volumetric molar concentration of tetrabutyl titanate is 0.125mol/L, and the volumetric molar concentration of potassium hydroxide is 2mol/L, and the volume radix of volumetric molar concentration is the volume of material in all introducing reactor inner bags;
5) the reactor inner bag that step 4) is disposed reaction mass places reactor, sealing, carried out hydrothermal treatment consists in 24 hours 120 ℃ of lower insulations, then allow reactor naturally cool to room temperature, with deionized water and dehydrated alcohol repetitive scrubbing reaction product, filter, dry, obtain tetragonal-phase barium titanate BaTiO
3Hollow is nanocrystalline, and size is 20-100 nm.
Claims (4)
1. tetragonal-phase barium titanate BaTiO
3The preparation method that hollow is nanocrystalline is characterized in that may further comprise the steps:
1) in tetrabutyl titanate, adds deionized water, sequestrant and hydrolysis inhibitor, normal pressure and 50-80 ℃ of lower the stirring 4-24 hour, the pH value of control reactant is 2-3, obtain the water-soluble colloidal sol of titaniferous, the mol ratio of tetrabutyl titanate, deionized water, sequestrant and hydrolysis inhibitor is 1:150 ~ 300:0.1 ~ 0.6:0.01 ~ 0.04, described sequestrant is the one or both combination in quadrol and the methyl ethyl diketone, and hydrolysis inhibitor is the one or both combination in hydrochloric acid and the nitric acid;
2) take by weighing barium acetate by barium acetate and tetrabutyl titanate mol ratio 3:1 metering, barium acetate is added in the deionized water, fully stir, form the aqueous solution of barium acetate;
3) potassium hydroxide being dissolved in deionized water, with step 2) aqueous solution of the barium acetate that makes joins potassium hydroxide aqueous solution, joins in the water-soluble colloidal sol of titaniferous of step 1) again, obtains containing the suspension of the oxyhydroxide precipitation of barium and titanium;
The suspension that 4) will contain the oxyhydroxide precipitation of barium and titanium is transferred in the reactor inner bag, reach the 70%-90% of reactor inner bag volume with the reaction mass volume in the deionized water conditioned reaction still inner bag, stirred at least 10 minutes, in the reaction mass, the volumetric molar concentration of barium acetate is 0.375 mol/L, the volumetric molar concentration of tetrabutyl titanate is 0.125mol/L, and the volumetric molar concentration of potassium hydroxide is 2 ~ 4 mol/L, and the volume radix of volumetric molar concentration is the volume of material in all introducing reactor inner bags;
5) the reactor inner bag that step 4) is disposed reaction mass places reactor, sealing, carried out hydrothermal treatment consists in 6-24 hour 120 ℃-240 ℃ lower insulations, then allow reactor naturally cool to room temperature, with deionized water and dehydrated alcohol repetitive scrubbing reaction product, filter, dry, obtain tetragonal-phase barium titanate BaTiO
3Hollow is nanocrystalline.
2. tetragonal-phase barium titanate BaTiO according to claim 1
3The preparation method that hollow is nanocrystalline is characterized in that reactor is polytetrafluoroethylliner liner, the reactor that the stainless steel external member is airtight.
3. described tetragonal-phase barium titanate BaTiO according to claim 1
3The preparation method that hollow is nanocrystalline is characterized in that the purity of said barium acetate, tetrabutyl titanate, potassium hydroxide, quadrol, methyl ethyl diketone and dehydrated alcohol all is not less than chemical pure.
4. tetragonal-phase barium titanate BaTiO according to claim 1
3The preparation method that hollow is nanocrystalline is characterized in that resulting tetragonal-phase barium titanate BaTiO
3The nanocrystalline size of hollow is 20-100 nm.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104402044A (en) * | 2014-11-14 | 2015-03-11 | 浙江大学 | Preparation method for barium titanate/graphene composite nanometer material |
| CN106178008A (en) * | 2016-07-06 | 2016-12-07 | 中山大学 | A kind of ultrasonic piezoelectricity Synergistic biocidal technology |
| CN107151029A (en) * | 2017-04-28 | 2017-09-12 | 长安大学 | A kind of sol gel synthesis preparation technology of tetra phase barium titanate powder |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2010110331A1 (en) * | 2009-03-27 | 2010-09-30 | 日立金属株式会社 | Semiconductor ceramic composition, heat generating element, and heat generating module |
| CN102249669A (en) * | 2010-11-04 | 2011-11-23 | 耿世达 | Preparation method of nanometer high-purity barium titanate |
| CN102276255A (en) * | 2011-06-02 | 2011-12-14 | 西北工业大学 | Preparation method for sheet-like barium titanate microcrystalline powder |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2010110331A1 (en) * | 2009-03-27 | 2010-09-30 | 日立金属株式会社 | Semiconductor ceramic composition, heat generating element, and heat generating module |
| CN102249669A (en) * | 2010-11-04 | 2011-11-23 | 耿世达 | Preparation method of nanometer high-purity barium titanate |
| CN102276255A (en) * | 2011-06-02 | 2011-12-14 | 西北工业大学 | Preparation method for sheet-like barium titanate microcrystalline powder |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104402044A (en) * | 2014-11-14 | 2015-03-11 | 浙江大学 | Preparation method for barium titanate/graphene composite nanometer material |
| CN104402044B (en) * | 2014-11-14 | 2016-01-20 | 浙江大学 | A kind of preparation method of barium titanate/graphene composite nano material |
| CN106178008A (en) * | 2016-07-06 | 2016-12-07 | 中山大学 | A kind of ultrasonic piezoelectricity Synergistic biocidal technology |
| CN107151029A (en) * | 2017-04-28 | 2017-09-12 | 长安大学 | A kind of sol gel synthesis preparation technology of tetra phase barium titanate powder |
| CN107151029B (en) * | 2017-04-28 | 2019-01-15 | 长安大学 | A kind of sol-gel self-combustion synthesis preparation process of tetra phase barium titanate powder |
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