CN101786654A - Method for preparing nanometer barium-strontium titanate powder - Google Patents
Method for preparing nanometer barium-strontium titanate powder Download PDFInfo
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- CN101786654A CN101786654A CN 201010117966 CN201010117966A CN101786654A CN 101786654 A CN101786654 A CN 101786654A CN 201010117966 CN201010117966 CN 201010117966 CN 201010117966 A CN201010117966 A CN 201010117966A CN 101786654 A CN101786654 A CN 101786654A
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Abstract
The invention discloses a method for preparing nanometer barium-strontium titanate powder, and aims to solve the technical problem that the barium-strontium titanate powder prepared by the conventional preparation method is big in grain size, uneven in grain size distribution and impure in crystal phase. The technical scheme comprises the following steps of: adding barium acetate, strontium acetate, tetrebutyl titanate, sodium oleate, oleic acid, normal butyl alcohol and sodium hydroxide in a hydrothermal kettle, heating the materials to react the materials, using ethanol to wash the mixture to obtain a precipitate, dissolving the precipitate in cyclohexane, adding ethanol into the mixed solution for reaction at room temperature to obtain a nanocrystalline BST precipitate, performing centrifugal separation of the nanocrystalline BST precipitate, using the ethanol to wash the residual oleic acid, and air-drying the precipitate at room temperature. In the invention, the barium-strontium titanate powder is prepared by a liquid-solid solution method, the grain size of the barium-strontium titanate powder by the method is reduced from 50 nanometers in the prior art to 10 to 25 nanometers, the grain size distribution is uniform, and the crystal phase purity is also improved.
Description
Technical field
The present invention relates to the preparation method of a kind of strontium-barium titanate (hereinafter to be referred as BST) powder, particularly a kind of preparation method of nano barium-strontium titanate powder.
Background technology
The ferroelectric thick film material is a kind of cheap novel dielectric tuning material, can be operated in radio-frequency range, has certain anti-bad electromagnetic environment ability again.Its advantage is: on the one hand, thick-film material reduces greatly than body material thickness, and required driving voltage also reduces greatly, can be used for microwave circuits; On the other hand, thick-film material has lower surface stress than thin-film material, and the dielectric characteristics and the resistance of aging of material are guaranteed, and has improved the viability of phase shifter in bad electromagnetic environment.Strontium-barium titanate (Ba1-xSrxTiO3) series of solid solutions is the big and low candidate material that is considered to ferroelectric phase shifter of lossy microwave owing to its microwave-tuned rate.Yet, prepare thick-film material, at first must the high-quality ceramic powder particle of preparation.That is to say that in order to reduce the sintering temperature of thick-film material, improve the density of material, the powder that is adopted all is even-grained nano-powder.
Document " I.Packia Selvam; V.Kumar; Synthesis of nanopowders of (Ba1_xSrx) TiO3; Materials Letters 56 (2002) 1089-1092 " discloses a kind of method of the BST of preparation powder, this method adopts the precursor aqua-solution method to prepare the BST powder, but the BST powder granularity that obtains is bigger, more than 50nm, and size-grade distribution inequality, and contain some carbonate dephasigns in the XRD figure spectrum demonstration powder, therefore also do not reach the purpose of industrialized production and use.
Summary of the invention
Big and skewness, the impure deficiency of crystalline phase for the barium-strontium titanate powder granularity that overcomes art methods preparation, the invention provides a kind of preparation method of nano barium-strontium titanate powder, adopt the barium-strontium titanate powder of liquid-solid solution method preparation can reduce its granularity, and even particle size distribution, and can improve the crystalline phase of barium-strontium titanate powder.
The technical solution adopted for the present invention to solve the technical problems: a kind of preparation method of nano barium-strontium titanate powder, be prepared from by barium acetate, strontium acetate, tetra-n-butyl titanate, sodium oleate, oleic acid, propyl carbinol and sodium hydroxide, be characterized in comprising the steps:
(a) with analytical pure level barium acetate: strontium acetate: tetra-n-butyl titanate is weighing in 3: 2: 15 in molar ratio, add in the stainless steel hydro-thermal still, again with distilled water: oleic acid: propyl carbinol added in 1: 3: 2 by volume, add sodium oleate then, the quality of sodium oleate accounts for 3%～5% of solid mixture, concentration is the sodium hydroxide of 4～8mol/L, stainless steel hydro-thermal still is moved on in the hydro-thermal stove gently reacting by heating 18～25h under 100～150 ℃ of conditions;
(b) step (a) gained mixed solution naturally cools to room temperature, remove supernatant liquid after, wash out throw out with ethanol, the ethanol consumption is advisable throw out can be washed out, hexanaphthene dissolution precipitation thing is used in centrifugation then, and the hexanaphthene consumption is advisable with dissolution precipitation thing just;
(c) add ethanol in step (b) gained mixing solutions, the ethanol consumption no longer increases to suitablely to generate sedimentary amount, produces the nano-crystalline BST precipitation under the room temperature;
(d), up to clean residual oleic acid, dry under the room temperature with the ethanol repetitive scrubbing with the nano-crystalline BST precipitation and centrifugal separation.
The invention has the beneficial effects as follows: because liquid-solid solution method prepares barium-strontium titanate powder, thereby shortcoming such as avoided causing that easily grain growth and impurity are sneaked in the prior art for preparing process, be reduced to 10～25nm more than the 50nm of barium-strontium titanate powder granularity by prior art, and even particle size distribution, crystalline phase purity is improved.
Below in conjunction with drawings and Examples the present invention is elaborated.
Description of drawings
Fig. 1 is the XRD figure of the prepared BST nano-powder of different concns mineralizer solution when adopting the BST powder of the inventive method preparation.
Fig. 2 is the TEM picture of the BST powder of embodiment 1 preparation.
Fig. 3 is the TEM picture of the BST powder of embodiment 3 preparations.
Embodiment
Embodiment 1, with the white Ba (Ac) of analytical pure level
20.75Mol/L, crystalloid Sr (Ac)
21/2H
2O0.5mol/L, distilled water 5mL, the sodium hydroxide of 4mol/L, 1.0g sodium oleate, 15mL oleic acid, 10mL butanols and 1.25mol/L positive four butyl esters of metatitanic acid be added in the stainless steel hydro-thermal still of Teflon inner bag, move on to gently then in the hydro-thermal stove, at 160 ℃ of following reacting by heating 24h.Reacted mixed solution is naturally cooled to room temperature, remove supernatant liquid, wash out the reaction precipitation thing with 25ml ethanol, the ethanol consumption is advisable precipitation can be washed out.Hexanaphthene dissolution precipitation thing is used in centrifugation then, and the hexanaphthene consumption is advisable with dissolution precipitation thing just.The ethanol that adds 35ml in this solution, the ethanol consumption no longer increases to suitablely to generate sedimentary amount, produces the nano-crystalline BST precipitation under the room temperature.With precipitation and centrifugal separation,, dry under the room temperature up to clean residual oleic acid with the ethanol repetitive scrubbing, obtain nanometer BST powder.The nanometer BST powder that obtains carries out surface topography and material phase analysis with Hitach S-530 scanning electron microscope, X ' pert Pro X-ray diffractometer.
As can be seen from Figure 1, along with the increase of NaOH concentration, the intensity of diffraction peak strengthens to some extent, and the particle of this explanation powder increases to some extent with the increase of NaOH concentration.Diffraction peak has certain broadening as can be seen simultaneously, and this mainly is because the too little reason of powder granule.Its crystalline structure is typical cubic perovskite structure, and product is purer.
As can be seen from Figure 2, its pattern is a cube phase structure.Granularity is less, about 10nm.
The grain size of calculating according to XRD and the grain size of TEM observation see Table 1, and as can be seen from Table 1, XRD calculation result is basic and the tem observation result is basic identical, and crystallographic dimension increases with the increase of mineralizer concentration.
Embodiment 2, with the white Ba (Ac) of analytical pure level
21.5Mol/L, crystalloid Sr (Ac)
21/2H
2O 1mol/L, distilled water 10mL, the sodium hydroxide of 5mol/L, positive four butyl esters of the metatitanic acid of 2.0g sodium oleate, 30mL oleic acid, 20mL butanols and 2.5mol/L are added in the stainless steel hydro-thermal still of Teflon inner bag, move on to gently then in the hydro-thermal stove, at 100 ℃ of following reacting by heating 25h.Reacted mixed solution is naturally cooled to room temperature, remove supernatant liquid, wash out the reaction precipitation thing with 30ml ethanol, the ethanol consumption is advisable precipitation can be washed out.Hexanaphthene dissolution precipitation thing is used in centrifugation then, and the hexanaphthene consumption is advisable with dissolution precipitation thing just.The ethanol that adds 40ml in this solution, the ethanol consumption no longer increases to suitablely to generate sedimentary amount, produces the nano-crystalline BST precipitation under the room temperature.With precipitation and centrifugal separation,, dry under the room temperature up to clean residual oleic acid with the ethanol repetitive scrubbing, obtain nanometer BST powder.The nanometer BST powder that obtains carries out surface topography and material phase analysis with Hitach S-530 scanning electron microscope, X ' pert Pro X-ray diffractometer.
As can be seen from Figure 1, when mineralizer concentration was 5mol/L, the intensity of diffraction peak strengthened to some extent, and the particle of this explanation powder increases to some extent with the increase of NaOH concentration.In addition, crystalline structure is purer typical cubic perovskite structure.
The grain size of calculating according to XRD and the grain size of TEM observation see Table 1, and as can be seen from Table 1, XRD calculation result is basic and the tem observation result is basic identical, compare during for 4mol/L with mineralizer concentration, and crystallographic dimension slightly increases.
Embodiment 3, with the white Ba (Ac) of analytical pure level
22.25Mol/L, crystalloid Sr (Ac)
21/2H
2O1.5mol/L does not contain CO
2Distilled water 15mL, the sodium hydroxide of 6mol/L, positive four butyl esters of the metatitanic acid of 3.0g sodium oleate, 45mL oleic acid, 30mL butanols and 3.75mol/L are added in the stainless steel hydro-thermal still of Teflon inner bag, move on to gently then in the hydro-thermal stove, at 150 ℃ of following reacting by heating 18h.Reacted mixed solution is naturally cooled to room temperature, remove supernatant liquid, wash out the reaction precipitation thing with 40ml ethanol, the ethanol consumption is advisable precipitation can be washed out.Hexanaphthene dissolution precipitation thing is used in centrifugation then, and the hexanaphthene consumption is advisable with dissolution precipitation thing just.The ethanol that adds 45ml in this solution, the ethanol consumption no longer increases to suitablely to generate sedimentary amount, produces the nano-crystalline BST precipitation under the room temperature.With precipitation and centrifugal separation,, dry under the room temperature up to clean residual oleic acid with the ethanol repetitive scrubbing, obtain nanometer BST powder.The nanometer BST powder that obtains carries out surface topography and material phase analysis with Hitach S-530 scanning electron microscope, X ' pert Pro X-ray diffractometer.
As can be seen from Figure 1, the particle of powder further increases with the increase of NaOH concentration.But crystalline structure is typical cubic perovskite structure still, and product is purer.
As can be seen from Figure 3, its pattern is a cube phase structure.Granularity is about 15nm.
As can be seen from Table 1, XRD calculation result is basic and the tem observation result is basic identical, and crystallographic dimension increases with the increase of mineralizer concentration.
Embodiment 4, with the white Ba (Ac) of analytical pure level
23Mol/L, crystalloid Sr (Ac)
21/2H
2O 2mol/L, distilled water 20mL, the sodium hydroxide of 8mol/L, positive four butyl esters of the metatitanic acid of 5.0g sodium oleate, 60mL oleic acid, 40mL butanols and 5mol/L are added in the stainless steel hydro-thermal still of Teflon inner bag, move on to gently then in the hydro-thermal stove, at 130 ℃ of following reacting by heating 20h.Reacted mixed solution is naturally cooled to room temperature, remove supernatant liquid, wash out the reaction precipitation thing with 45ml ethanol, the ethanol consumption is advisable precipitation can be washed out.Hexanaphthene dissolution precipitation thing is used in centrifugation then, and the hexanaphthene consumption is advisable with dissolution precipitation thing just.The ethanol that adds 50ml in this solution, the ethanol consumption no longer increases to suitablely to generate sedimentary amount, produces the nano-crystalline BST precipitation under the room temperature.With precipitation and centrifugal separation,, dry under the room temperature up to clean residual oleic acid with the ethanol repetitive scrubbing, obtain nanometer BST powder.The nanometer BST powder that obtains carries out surface topography and material phase analysis with Hitach S-530 scanning electron microscope, X ' pert Pro X-ray diffractometer.
As can be seen from Figure 1, when mineralizer concentration is 8mol/L, the trend that the particle that powder still arranged increases with the increase of NaOH concentration, but increase and few.Crystalline structure still is purer typical cubic perovskite structure.
As can be seen from Table 1, XRD calculation result is basic and the tem observation result is basic identical, and crystallographic dimension increases with the increase of mineralizer concentration.
The grain size of grain size that table 1XRD calculates and TEM observation
| Embodiment | ??Ba/Ti | ??NaOH(mol/L) | ?Calculated?size(nm) | ?Observed?size(nm) |
| ??1 | ??3∶2 | ??4 | ??10.7 | ??10-12 |
| ??2 | ??3∶2 | ??5 | ??12.0 | ??10-15 |
| ??3 | ??3∶2 | ??6 | ??16.7 | ??15-20 |
| Embodiment | ??Ba/Ti | ??NaOH(mol/L) | ?Calculated?size(nm) | ?Observed?size(nm) |
| ??4 | ??3∶2 | ??8 | ??18.2 | ??15-25 |
In a word, the present invention selects different mineralizer concentration, by liquid-solid solution method, with cheap Costco Wholesale, convenient feasible technology prepare successfully that granularity is little and even, good dispersity, strontium-barium titanate nano-powder that purity is high, therefore suitable industrialization promotion of strontium-barium titanate nano-powder of the present invention and scale operation.
Claims (1)
1. the preparation method of a nano barium-strontium titanate powder is prepared from by barium acetate, strontium acetate, tetra-n-butyl titanate, sodium oleate, oleic acid, propyl carbinol and sodium hydroxide, is characterized in comprising the steps:
(a) with analytical pure level barium acetate: strontium acetate: tetra-n-butyl titanate is weighing in 3: 2: 5 in molar ratio, add in the stainless steel hydro-thermal still, again with distilled water: oleic acid: propyl carbinol added in 1: 3: 2 by volume, add sodium oleate then, the quality of sodium oleate accounts for 3%～5% of solid mixture, concentration is the sodium hydroxide of 4～8mol/L, stainless steel hydro-thermal still is moved on in the hydro-thermal stove gently reacting by heating 18～25h under 100～150 ℃ of conditions;
(b) step (a) gained mixed solution naturally cools to room temperature, remove supernatant liquid after, wash out throw out with ethanol, the ethanol consumption is advisable throw out can be washed out, hexanaphthene dissolution precipitation thing is used in centrifugation then, and the hexanaphthene consumption is advisable with dissolution precipitation thing just;
(c) add ethanol in step (b) gained mixing solutions, the ethanol consumption no longer increases to suitablely to generate sedimentary amount, produces the nano-crystalline BST precipitation under the room temperature;
(d), up to clean residual oleic acid, dry under the room temperature with the ethanol repetitive scrubbing with the nano-crystalline BST precipitation and centrifugal separation.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106757351A (en) * | 2016-11-18 | 2017-05-31 | 西南石油大学 | A kind of preparation method of barium strontium titanate crystal beam material |
| CN109759047A (en) * | 2019-03-20 | 2019-05-17 | 南京工业大学 | A kind of preparation method of barium strontium aerogels |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0908423A1 (en) * | 1997-10-09 | 1999-04-14 | Murata Manufacturing Co., Ltd. | Barium titanate semiconductive ceramic |
| US20030133869A1 (en) * | 2002-01-15 | 2003-07-17 | Samsung Electro-Mechanics Co., Tld. | Method for preparing barium titanate powder by oxalate synthesis |
| CN1683276A (en) * | 2005-03-13 | 2005-10-19 | 中国科学院青海盐湖研究所 | Process for hydro-thermally synthesizing strontium-barium titanate ceramic powder at normal atmosphere |
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2010
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0908423A1 (en) * | 1997-10-09 | 1999-04-14 | Murata Manufacturing Co., Ltd. | Barium titanate semiconductive ceramic |
| US20030133869A1 (en) * | 2002-01-15 | 2003-07-17 | Samsung Electro-Mechanics Co., Tld. | Method for preparing barium titanate powder by oxalate synthesis |
| CN1683276A (en) * | 2005-03-13 | 2005-10-19 | 中国科学院青海盐湖研究所 | Process for hydro-thermally synthesizing strontium-barium titanate ceramic powder at normal atmosphere |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106757351A (en) * | 2016-11-18 | 2017-05-31 | 西南石油大学 | A kind of preparation method of barium strontium titanate crystal beam material |
| CN109759047A (en) * | 2019-03-20 | 2019-05-17 | 南京工业大学 | A kind of preparation method of barium strontium aerogels |
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