CN1212997C - Preparation method of barium strontium titanate ultra-fine powder - Google Patents
Preparation method of barium strontium titanate ultra-fine powder Download PDFInfo
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- CN1212997C CN1212997C CN 03150835 CN03150835A CN1212997C CN 1212997 C CN1212997 C CN 1212997C CN 03150835 CN03150835 CN 03150835 CN 03150835 A CN03150835 A CN 03150835A CN 1212997 C CN1212997 C CN 1212997C
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Abstract
The present invention relates to a method for preparing barium strontium titanate (BST) superfine powder materials, which belongs to the field of the preparation of electronic ceramic powder. Precursor solution is prepared by using tetrabutyl titanate, ammonia water, citric acid, barium nitrate and strontium nitrate as raw materials according to the chemical formula of Ba<1-x>SrxTiO3, wherein the molar ratio of Ba to Sr to Ti is (1-x): x: 1 (0<x<1). Three kinds of solution is mixed, ethylene alcohol is added to prevent powder materials from producing agglomeration in the process of gelatination, and the mixed solution is heated in a water bath of 70 DEG C to form collosol; then the collosol is dried into dried gelatin under the condition of a vacuum of 120 DEG C; finally, the dried gelatin is calcined at a temperature of 500 to 800 DEG C, and the superfine powder with good dispersivity, uniform grain size and narrow grain size distribution (35 to 45 nm) is prepared, wherein the average grain diameter of the superfine powder is 40 nm. BST ceramics prepared by the powder have low sintering temperature and good electrical property.
Description
Affiliated field
The invention relates to the preparation method of strontium-barium titanate (BST) nanometer scale superfine powder, this method is different from the preparation of traditional BST nano-powder, unique reagent---citric acid is that intercalating agent forms clarifying colloidal sol and adopt, employing ethylene glycol is dispersion agent, prepares the BST powder by sol-gel process.Belong to the ceramic powder preparation field.
Background technology
Compare with numerous powder preparing methods, sol-gel method prepares powder, and to have a polyvoltine group member mixing uniformity good, and plurality of advantages such as stoichiometric ratio is controlled easily, and equipment is simple has been widely used in the preparation of novel powder.Yet, prepare in the BST materials process at existing sol-gel process, all use acetate solution basically, form colloidal sol by simple complexing process, drying changes gel into again, obtains the BST powder at the temperature lower calcination that is higher than 1000 ℃ at last.The powder of Huo Deing is reunited seriously usually like this, and particle is bigger, institute's synthetic powder sintering temperature height, and the ceramic granularity that obtains is big, has influenced raising (Journal of Inorganic Materials, 1998,13 (3), the 389-395 of material property; Journal of Inorganic Materials, 1999,14 (1), 101-106).Therefore, explore new preparation method, reduce the synthesis temperature of BST, and then further reduce the sintering temperature of BST pottery,, become the technology focus in this field to improve the material final properties.
Summary of the invention
The object of the present invention is to provide a kind ofly to prepare the novel method of BST powder with precursor solution, this method is to develop on Pechini method (M.P.Pechini, U.S.Patent No.3 330,697, July, 1967) principle basis.Select for use citric acid to form clarifying colloidal sol as sequestrant, and treated xerogel is because of containing citric acid and nitrate radical, also have combustible characteristics, extra heat energy is provided, therefore can have made xerogel (about 800 ℃) calcining under lower temperature obtain the ultra-fine BST powder of complete crystallization.Utilize the Tc of the prepared BST of synthetic technology of the present invention to hang down 600-700 ℃, hang down 200-300 ℃ than the Tc of collosol and gel non-combustion method product than the Tc of conventional solid-state method synthetic product.The reduction significantly of Tc is of value to the formation superfine powder.And adopt BST ultrafine powder provided by the invention can finally improve the sintering character of stupalith, and reduce the sintering temperature of material, improve its density, obtain close grain (average crystal grain 1 μ m) BST pottery, thereby improve the electrical property of material.
A kind of precursor mixing solutions provided by the invention is to be raw material with tetrabutyl titanate, ammoniacal liquor, citric acid, nitrate of baryta, strontium nitrate.Be configured to barium, strontium, citric acid unit solution that the titanium three is stable earlier, principle that mixes by similar person and the stoichiometric ratio binary precursor aqueous solution that mixes required Ba/Sr ratio afterwards, add titaniferous unit solution at last, be configured to the ternary precursor aqueous solution of Ba/Sr/Ti, Ba, Sr, three kinds of element mol ratios of Ti are 1-X: X: 1,0＜X＜1 wherein.The pH value of regulating ternary forerunner mixing solutions with ammoniacal liquor is between the 6-7, is dispersion agent with ethylene glycol.Add-on and Ti element mol ratio by ethylene glycol are 1-5: 1 mixed mixes.In 70 ℃ of heating in water bath, make the solution that mixes solution become colloidal sol, under 120 ℃ of vacuum conditions, be dried into xerogel then.The BST xerogel after 300 mesh sieves, obtains nanometer scale BST superfine powder 400-800 ℃ of calcination processing.Technical process is referring to Fig. 1.
The calcining temperature of BST xerogel can obtain the BST crystalline powder at the temperature lower calcination that is higher than 500 ℃ in 500-800 ℃ of scope, then can obtain the BST powder (see figure 2) of complete crystallization 800 ℃ of following calcinings.Interpolation tensio-active agent ethylene glycol has obviously reduced the reunion degree of synthetic powder, and the powder median size is reduced to about about 40nm from about 100nm, obtains superfine nano magnitude BST powder.This powder compression molding after 1300 ℃ of pressureless sintering, forms the dense sintering body of the about 1 μ m of average crystal grain.The specific inductivity of sintered sample is 1470, dielectric loss be 0.006 (25 ℃, 10KHz).
Superfine powder preparation method provided by the invention has easy and simple to handle, and the characteristics of good stability can obtain the BST powder of complete crystallization 800 ℃ of following processing, and powder size is little.With prepared powder compression molding, can obtain dense sintering body (seeing Fig. 3, the about 1um of average crystal grain) at 1300 ℃ of pressureless sintering 2h
Description of drawings
Figure 1B ST superfine powder preparation technology schema.
The capable figure that penetrates of Fig. 2 gained BST superfine powder X.
The sintered compact SEM photo of 300 ℃ of 2h pressureless sinterings of Figure 31.
Figure 44 0nm left and right sides BST powder SEM photo.
Figure 51 00nm left and right sides BST powder SEM photo.
Embodiment
Embodiment 1: the effect of adding dispersion agent ethylene glycol
Preparation ternary forerunner mixing solutions: during preparation barium citrate solution, at first regulate citric acid solution to pH=6-7 with ammoniacal liquor.The citric acid solution CA (citric acid) of mixed nitrate barium and ammonification: Ba then
2+(metal ion)=2: 1 (mol ratio); When preparation strontium citrate solution, directly mix citric acid solution and strontium nitrate solution CA (citric acid): Sr
2+(metal ion)=2: 1 (mol ratio); When preparation citric acid titanium solution, by the 1g citric acid: the ratio of 1g tetrabutyl titanate, with the 0.2mol tetrabutyl titanate be added to concentration be 50%, and the citric acid solution that regulates in advance in (pH=6), constantly stirring, 70 ℃ of heating in water bath make resolution of precipitate.Leave standstill a moment, it is two-layer up and down that solution is divided into.With separating funnel the citric acid titanium solution of lower floor is separated.
According to chemical formula Ba
0.5Sr
0.5TiO
3Mix the barium citrate and the strontium citrate solution that have prepared, and then add the citric acid titanium solution.The pH value of regulating ternary forerunner mixing solutions with ammoniacal liquor is between the 6-7, adds dispersion agent ethylene glycol to prevent the reunion of powder in the follow-up gelation process.By ethylene glycol add-on and Ti element mol ratio is 2.5: 1 mixed, mixes.In 70 ℃ of heating in water bath, make the solution that mixes solution become colloidal sol, become xerogel at 120 ℃ of vacuum dryings then.The BST xerogel 800 ℃ of calcinings, after 300 mesh sieves, is obtained the BST superfine powder (see figure 4) about granularity 40nm.
Embodiment 2: the contrast of not adding the ethylene glycol dispersion agent is implemented
Preparation ternary forerunner mixing solutions: during preparation barium citrate solution, at first regulate citric acid solution to pH=6-7 with ammoniacal liquor.The citric acid solution CA (citric acid) of mixed nitrate barium and ammonification: Ba then
2+(metal ion)=2: 1 (mol ratio); When preparation strontium citrate solution, directly mix citric acid solution and strontium nitrate solution CA (citric acid): Sr
2+(metal ion)=2: 1 (mol ratio); When preparation citric acid titanium solution, by the 1g citric acid: the ratio of 1g tetrabutyl titanate, with the 0.2mol tetrabutyl titanate be added to concentration be 50%, and the citric acid solution that regulates in advance in (pH=6), constantly stirring, 70 ℃ of heating in water bath make resolution of precipitate.Leave standstill a moment, it is two-layer up and down that solution is divided into.With separating funnel the citric acid titanium solution of lower floor is separated.
According to chemical formula Ba
0.5Sr
0.5TiO
3Mix the barium citrate and the strontium citrate solution that have prepared, and then add the citric acid titanium solution, and the pH value of maintenance mixing solutions is between the 6-7.In 70 ℃ of heating in water bath, make the solution that mixes solution become colloidal sol, under 120 ℃ of vacuum conditions, be dried into xerogel then.The BST xerogel 800 ℃ of calcination processing, after 300 mesh sieves, is obtained the BST superfine powder (see figure 5) about median size 100nm.
Claims (3)
1. the preparation method of a nanometer scale BST superfine powder comprises presoma preparation, sol-gel process and high-temperature calcination technological process, it is characterized in that:
(1) be raw material with tetrabutyl titanate, ammoniacal liquor, citric acid, nitrate of baryta, strontium nitrate, be configured to earlier the stable citric acid unit solution of baric, strontium, titanium respectively, afterwards principle that mixes by similar person and the stoichiometric ratio binary precursor aqueous solution that mixes required Ba/Sr ratio; Add titaniferous unit solution at last again, be configured to the ternary precursor aqueous solution of Ba/Sr/Ti, Ba, Sr, three kinds of element mol ratios of Ti are 1-X: X: 1,0＜X＜1 wherein;
(2) the pH value with ammoniacal liquor adjusting ternary forerunner mixing solutions is between the 6-7, adds ethylene glycol to prevent the reunion of powder in the follow-up gelation process; The add-on of ethylene glycol be 1-5 by Ti element mol ratio: 1 mixed, mix, in 70 ℃ of heating in water bath, make the solution that mixes solution become colloidal sol, under 120 ℃ of vacuum conditions, be dried into xerogel then; The BST xerogel after 300 mesh sieves, obtains nanometer scale BST superfine powder 400-800 ℃ of calcination processing.
2. by the preparation method of the described nanometer scale BST superfine powder of claim 1, it is characterized in that:
(1) when preparation barium citrate solution, at first regulate citric acid solution to pH=6-7 with ammoniacal liquor, the citric acid solution of mixed nitrate barium and own ammonification is pressed citric acid: Ba then
2+=2: 1 (mol ratio) mixed;
(2) when preparation strontium citrate solution, directly press citric acid: Sr
2+=2: 1 (mol ratio) mixed citric acid solution and strontium nitrate solution;
(3) when preparation citric acid titanium solution, in the 1g citric acid: the ratio of 1g tetrabutyl titanate, with the 0.2mol tetrabutyl titanate be added to concentration be 50%, and the citric acid solution of the pH=6 that regulates in advance in, constantly stir, 70 ℃ of heating in water bath make resolution of precipitate, leave standstill a moment, it is two-layer up and down that solution is divided into, and with separating funnel the citric acid titanium solution of lower floor separated again.
3. by claim 1 or 2 described nanometer scale BST superfine powder preparation methods, it is characterized in that: Ba in the precursor aqueous solution: Sr: Ti=0.5: 0.5: 1 (mol ratio); The BST xerogel obtains the BST superfine powder that median size is about 40nm 800 ℃ of calcination processing.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101705519B (en) * | 2009-11-19 | 2012-05-30 | 南京工业大学 | Barium strontium titanate ferroelectric nano single crystal particle and preparation method thereof |
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| CN1308498C (en) * | 2005-01-12 | 2007-04-04 | 中国科学院新疆理化技术研究所 | Microwave hydrothermal synthesis method for nanometer crystal strontium titanate barium |
| CN100378005C (en) * | 2005-11-16 | 2008-04-02 | 中国科学院上海硅酸盐研究所 | Process for preparing submicron grade barium strontium phthalate powder by packing method |
| CN102241509A (en) * | 2011-05-26 | 2011-11-16 | 中国科学院上海硅酸盐研究所 | Method for preparing barium strontium titanate nano powder |
| CN102584192B (en) * | 2012-02-02 | 2013-07-24 | 陕西科技大学 | Preparation method of bismuth ferrate barium titanate solid-solution-based composite material with high magnetization intensity and high resistivity |
| CN110590357A (en) * | 2019-08-16 | 2019-12-20 | 南方科技大学 | Preparation method of barium strontium titanate nano powder |
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| CN101705519B (en) * | 2009-11-19 | 2012-05-30 | 南京工业大学 | Barium strontium titanate ferroelectric nano single crystal particle and preparation method thereof |
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