CN101767818A - Ion-doped potassium bismuth titanate nano powder and preparation method thereof - Google Patents

Ion-doped potassium bismuth titanate nano powder and preparation method thereof Download PDF

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CN101767818A
CN101767818A CN201010023082A CN201010023082A CN101767818A CN 101767818 A CN101767818 A CN 101767818A CN 201010023082 A CN201010023082 A CN 201010023082A CN 201010023082 A CN201010023082 A CN 201010023082A CN 101767818 A CN101767818 A CN 101767818A
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bismuth
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nano powder
potassium
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赵苏串
何敏
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University of Shanghai for Science and Technology
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University of Shanghai for Science and Technology
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Abstract

The invention relates to an ion-doped potassium bismuth titanate system nano powder and a preparation method thereof, and belongs to the technical field of piezoelectric materials. The molecular formula of the nano powder is BiO.5K0.5TiO3+upsilonMalphaObeta (upsilon is equal to 0-0.06; when M is Cu, Co, Sr or Ba, alpha is equal to 1, and beta is equal to 1; and when M is Bi, alpha is equal to 2, and beta is equal to 3). The preparation technique comprises the following steps: preparing a precursor solution by a sol-gel method by using butyl titanate, potassium nitrate, bismuth nitrate and metal salts of doped ions as the main raw materials, glycerin and glacial acetic acid as the solvent, and diacetone as the stabilizer; heating and stirring at about 60 DEG C for 2 hours to obtain the sol with stable performance; drying in a drying box at the constant temperature of 90 DEG C for 24 hours, wherein the gelation and gel drying are completed in one step; and sintering the dried gel powder in a crucible at 400-700 DEG C to obtain the ion-doped potassium bismuth titanate nano powder. The invention has the advantages of short synthesis period, low temperature for phase formation, simple technique, low cost, stable product quality and fine grains of nano powder (less than 20 nm).

Description

A kind of ion-doped potassium bismuth titanate nano powder and preparation method thereof
Technical field
The invention belongs to environmental harmony functional materials preparing technical field, particularly a kind of ion-doped potassium bismuth titanate nano powder and preparation method thereof.
Background technology
Piezoelectric can be realized the mutual conversion between mechanical energy and the electric energy, has many-sided character such as piezoelectricity, ferroelectric, photoelectricity and pyroelectricity, have in fields such as machinery, electronics, communications very and use widely, and be a kind of crucial functional materials.Pb-based lanthanumdoped zirconate titanates (Pb (Zr, Ti) O 3Be called for short PZT) owing to its excellent piezoelectric property is occupied an leading position at aspects such as transmitter, driving mechanism, transmodulators always, yet plumbous oxide among the PZT (PbO) accounts for about 70% of raw material total amount, PbO is a volatile material under a kind of deleterious, high temperature, environment is produced burden, serious harm human health.Therefore the piezoelectric that develops unleaded environment compatibility be one urgent and have a problem of great Practical significance.
Bismuth potassium titanate (K 0.5Bi 0.5TiO 3, be called for short KBT) and genus tetragonal when room temperature, the bismuth-sodium titanate (Na more with present research 0.5Bi 0.5TiO 3, be called for short NBT) and belong to the composite mixed uhligite ferroelectrics in A position.The KBT Curie temperature is up to 380 ℃, coercive electric field lower (Ec=1.5kV/mm), so KBT has at room temperature wideer temperature and use interval and lower polarization difficulty, and embodied under hot conditions alternative lead base material (as PbTiO 3, PbZrO 3Deng) potentiality.Traditional technology preparation pottery is based on high temperature solid state reaction mechanism, and the powder granule that obtains is thick (micron order).KBT is difficult to sintering, and normal with the dephasign that is difficult to eliminate in the product, makes that the preparation of high-compactness KBT pottery and piezoelectric property research are less.In recent years, sol-gel (sol-gel) method since in the material various components can realize the uniform mixing of atom or molecular level, can make the material of height even compact, making the attention that is subjected to people aspect the fine ceramics.
Summary of the invention
The objective of the invention is to have announced a kind of by the sol-gel legal system pure perovskite phase of having got everything ready, ion-doped potassium bismuth titanate nano powder of uniform particle diameter tiny (less than 20nm) and preparation method thereof is for the preparation and the research of high-compactness KBT base function ceramics creates conditions.
The present invention is realized by following technical scheme:
The prepared ion-doped potassium bismuth titanate nano powder of the present invention is made up of titanium, bismuth, potassium, copper, cobalt, strontium, barium, oxonium ion, has the nano-powder material of perovskite structure.Its molecular formula is Bi 0.5K 0.5TiO 3+ uM αO β(u=0～0.06; When M=Cu, Co, Sr, Ba, α=β=1; During M=Bi, α=2, β=3).
Preparation technology of the present invention is as follows successively:
(1) configuration solution in early stage, early stage, solution was a kind of of following situation:
1. pure bismuth potassium titanate Bi 0.5K 0.5TiO 3Solution, promptly the stoichiometric ratio by molecular formula accurately takes by weighing five water Bismuth trinitrates during u=0, saltpetre is dissolved in the mixed solution of glacial acetic acid, deionized water and glycerol, continues heating and constantly stirs, and temperature is controlled at 50 ℃～70 ℃, until dissolving fully.Make solution 1#.
2. the bismuth potassium titanate of ion doping is Bi 0.5K 0.5TiO 3+ uM αO βSolution, promptly 0＜u≤0.06 o'clock accurately takes by weighing five water Bismuth trinitrates, saltpetre and nitric acid M by the stoichiometric ratio of molecular formula or acetic acid M (M is any one in bismuth, copper, cobalt, strontium or the barium element) is dissolved in the mixed solution of glacial acetic acid, deionized water and glycerol, continue heating and constantly stirring, temperature is controlled at 50 ℃～70 ℃, until dissolving fully.Make solution 1#.
(2) accurately measure tetrabutyl titanate and add an amount of methyl ethyl diketone by the stoichiometric ratio of molecular formula and make stablizer, at room temperature stir, make solution 2#.Select a kind of of solution in early stage, slowly pour 2# solution into 1# solution,, obtain the colloidal sol of transparent and stable at 50 ℃～70 ℃ following abundant heated and stirred 2h.
(3) gained colloidal sol freeze-day with constant temperature 24h in 90 ℃ of loft drier is obtained xerogel.
(4) with the xerogel grinding powder, be placed on that the temperature rise rate with 3 ℃/min rises to 400 ℃～700 ℃ in the crucible, furnace cooling behind the insulation 2h obtains the potassium bismuth titanate nano powder of ion doping.
The invention has the beneficial effects as follows: adopt five water Bismuth trinitrates, saltpetre and tetrabutyl titanate as main raw material, wherein five water Bismuth trinitrates need not be removed crystal water, make preparation process few, and technology is simple.Saltpetre is insoluble to common organic solvents (as glacial acetic acid etc.), and draw it according to a large amount of experiments and be dissolved in deionized water and glycerol, and determined that the ratio of organic solvent is as follows: tetrabutyl titanate and methyl ethyl diketone mol ratio are 1: 1～1: 2; Glacial acetic acid and deionized water volume ratio are 3: 1; Required glycerol volume is smaller or equal to the volume of required deionized water.Technology of the present invention is reasonable, is convenient to operation, because the adding of glycerol makes colloidal sol more stable.Can finish in a step by colloidal sol system gel, Drying of gels, made things convenient for operation, shortened preparation cycle.Annealing temperature is low, and 500 ℃ of sintering basically form the uhligite phase, and 600 ℃ of sintering form the pure perovskite phases, has reduced about 200 ℃ than the sintering temperature (740 ℃～1000 ℃) of common solid reaction process synthetic powder, and has not had dephasign and produce.Temperature is brought up to 800 ℃, and system is the pure perovskite phase structure still, has illustrated that the sol-gel legal system is equipped with the thermally-stabilised regional broad of bismuth potassium titanate serial nano powder.And gained ion-doped potassium bismuth titanate nano powder product size homogeneous tiny (less than 20nm) is for condition has been created in the preparation and the research of ceramic component miniaturization.
Description of drawings
Fig. 1 is the XRD spectrum of differing temps annealed KBT nano-powder.
Fig. 2 is the TEM figure of KBT nano-powder under 740 ℃ of annealing conditions.
Fig. 3 is the XRD spectrum of the KBT nano-powder of ion doping.
Embodiment
The phase structure of powder (XRD) adopts the analysis of DLMAX-2200X x ray diffractometer x, adopts the particle size and the pattern of the prepared material of JEOL 200CX determination of transmission electron microscopy.
Embodiment 1
Dispose pure bismuth potassium titanate powder, promptly during u=0
(1) by molecular formula Bi 0.5K 0.5TiO 3Stoichiometric ratio accurately take by weighing raw material: five water Bismuth trinitrate 9.799g, saltpetre 2.043g are dissolved in the mixed solution of 30ml glacial acetic acid, 10ml deionized water and 10ml glycerol, continue heating and constantly stirring, temperature is controlled at 50 ℃～70 ℃, until dissolving fully.Make solution 1#.
(2) by molecular formula Bi 0.5K 0.5TiO 3Stoichiometric ratio accurately measure the 13.9ml tetrabutyl titanate and add the 5.0ml methyl ethyl diketone and make stablizer, at room temperature stir, make solution 2#.Slowly pour 2# solution into 1# solution,, obtain the colloidal sol of transparent and stable at 50 ℃～70 ℃ following abundant heated and stirred 2h.
(3) gained colloidal sol freeze-day with constant temperature 24h in 90 ℃ of loft drier is obtained xerogel.
(4) with the xerogel grinding powder, be placed on that the temperature rise rate with 3 ℃/min rises to 400 ℃, 500 ℃, 600 ℃, 700 ℃, 740 ℃ and 800 ℃ in the crucible, furnace cooling behind the insulation 2h obtains pure potassium bismuth titanate nano powder.
Embodiment 2
The bismuth potassium titanate of configuration Bi ion counter doping is a solution, and M=Bi in molecular formula is during u=0.06
(1) by molecular formula Bi 0.5K 0.5TiO 3+ uM αO βStoichiometric ratio accurately take by weighing raw material: five water Bismuth trinitrate 10.3874g, saltpetre 2.043g are dissolved in the mixed solution of 30ml glacial acetic acid, 10ml deionized water and 10ml glycerol, continue heating and constantly stirring, temperature is controlled at 50 ℃～70 ℃, until dissolving fully.Make solution 1#.
(2) by molecular formula Bi 0.5K 0.5TiO 3+ uM αO βStoichiometric ratio accurately measure the 13.9ml tetrabutyl titanate and add the 5.0ml methyl ethyl diketone and make stablizer, at room temperature stir, make solution 2#.Slowly pour 2# solution into 1# solution,, obtain the colloidal sol of transparent and stable at 50 ℃～70 ℃ following abundant heated and stirred 2h.
(3) gained colloidal sol freeze-day with constant temperature 24h in 90 ℃ of loft drier is obtained xerogel.
(4) with the xerogel grinding powder, be placed on that the temperature rise rate with 3 ℃/min rises to 740 ℃ in the crucible, furnace cooling behind the insulation 2h, the potassium bismuth titanate nano powder that obtains Bi compensation 6% is designated as sample a.
Embodiment 3
The bismuth potassium titanate of configuration Cu ion doping is a solution, and M=Cu in molecular formula is during u=0.01
(1) by molecular formula Bi 0.5K 0.5TiO 3+ uM αO βStoichiometric ratio accurately take by weighing raw material: five water Bismuth trinitrate 24.499g, saltpetre 5.106g, a hydrated copper acetate 0.202g are dissolved in the mixed solution of 75ml glacial acetic acid, 25ml deionized water and 10ml glycerol, continue heating and constantly stirring, temperature is controlled at 50 ℃～70 ℃, until dissolving fully.Make solution 1#.
(2) by molecular formula Bi 0.5K 0.5TiO 3+ uM αO βStoichiometric ratio accurately measure the 34.8ml tetrabutyl titanate and add the 12.5ml methyl ethyl diketone and make stablizer, at room temperature stir, make solution 2#.Slowly pour 2# solution into 1# solution,, obtain the colloidal sol of transparent and stable at 50 ℃～70 ℃ following abundant heated and stirred 2h.
(3) gained colloidal sol freeze-day with constant temperature 24h in 90 ℃ of loft drier is obtained xerogel.
(4) with the xerogel grinding powder, be placed on that the temperature rise rate with 3 ℃/min rises to 700 ℃ in the crucible, furnace cooling behind the insulation 2h, the potassium bismuth titanate nano powder that obtains Cu compensation 1% is designated as sample b.
Embodiment 4
The bismuth potassium titanate of configuration Co ion doping is a solution, and M=Co in molecular formula is during u=0.03
(1) by molecular formula Bi 0.5K 0.5TiO 3+ uM αO βStoichiometric ratio accurately take by weighing raw material: five water Bismuth trinitrate 24.499g, saltpetre 5.106g, cobalt nitrate hexahydrate 0.882g are dissolved in the mixed solution of 75ml glacial acetic acid and 25ml deionized water, continue heating and constantly stirring, temperature is controlled at 50 ℃～70 ℃, until dissolving fully.Make solution 1#.
(2) by molecular formula Bi 0.5K 0.5TiO 3+ uM αO βStoichiometric ratio accurately measure the 34.8ml tetrabutyl titanate and add the 12.5ml methyl ethyl diketone and make stablizer, at room temperature stir, make solution 2#.Slowly pour 2# solution into 1# solution,, obtain the colloidal sol of transparent and stable at 50 ℃～70 ℃ following abundant heated and stirred 2h.
(3) gained colloidal sol freeze-day with constant temperature 24h in 90 ℃ of loft drier is obtained xerogel.
(4) with the xerogel grinding powder, be placed on that the temperature rise rate with 3 ℃/min rises to 700 ℃ in the crucible, furnace cooling behind the insulation 2h, the potassium bismuth titanate nano powder that obtains Co compensation 3% is designated as sample c.

Claims (4)

1. ion-doped potassium bismuth titanate nano powder is characterized in that it is made up of titanium, bismuth, potassium, copper, cobalt, strontium, barium, oxonium ion, and its molecular formula is Bi 0.5K 0.5TiO 3+ uM αO β, wherein u is 0～0.06; M is any one in bismuth, copper, cobalt, strontium or the barium element, when M=Cu, Co, Sr, Ba, and α=β=1; When M=Bi, α=2, β=3.
2. the preparation method of an ion-doped potassium bismuth titanate nano powder as claimed in claim 1 is characterized in that preparation process is as follows:
(1) configuration solution in early stage, early stage, solution was a kind of of following situation:
1. pure bismuth potassium titanate Bi 0.5K 0.5TiO 3Solution, u=0
By molecular formula Bi 0.5K 0.5TiO 3Stoichiometric ratio accurately take by weighing five water Bismuth trinitrates, saltpetre is dissolved in the mixed solution of glacial acetic acid, deionized water and glycerol, continues heating and constantly stirs, temperature is controlled at 50～70 ℃, until dissolving fully, makes solution 1#;
2. the bismuth potassium titanate Bi of ion doping 0.5K 0.5TiO 3+ uM αO βSolution, 0＜u≤0.06
By molecular formula Bi 0.5K 0.5TiO 3+ uM αO βStoichiometric ratio accurately take by weighing five water Bismuth trinitrates, saltpetre and nitric acid M or acetic acid M is dissolved in the mixed solution of glacial acetic acid, deionized water and glycerol, wherein M is a kind of in bismuth, copper, cobalt, strontium or the barium element, continue heating and constantly stirring, temperature is controlled at 50～70 ℃, until dissolving fully, make solution 1#;
(2) by molecular formula Bi 0.5K 0.5TiO 3+ uM αO βStoichiometric ratio accurately measure tetrabutyl titanate and add an amount of methyl ethyl diketone and make stablizer, at room temperature stir, make solution 2#; Select a kind of of solution in early stage, slowly pour 2# solution into 1# solution,, obtain the colloidal sol of transparent and stable at 50～70 ℃ of following abundant heated and stirred 2h;
(3) gained colloidal sol freeze-day with constant temperature 24h in 90 ℃ of loft drier is obtained xerogel;
(4) with the xerogel grinding powder, be placed on that the temperature rise rate with 3 ℃/min rises to 400～700 ℃ in the crucible, furnace cooling behind the insulation 2h obtains the potassium bismuth titanate nano powder of ion doping.
3. the preparation method of ion-doped potassium bismuth titanate nano powder according to claim 2 is characterized in that tetrabutyl titanate and methyl ethyl diketone mol ratio are 1: 1～1: 2; Glacial acetic acid and deionized water volume ratio are 3: 1; Required glycerol volume is smaller or equal to the volume of required deionized water.
4. the preparation method of ion-doped potassium bismuth titanate nano powder according to claim 2 is characterized in that the ion-doped potassium bismuth titanate nano powder particle diameter is below 20nm.
CN201010023082A 2010-01-21 2010-01-21 Ion-doped potassium bismuth titanate nano powder and preparation method thereof Pending CN101767818A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105271380A (en) * 2015-10-31 2016-01-27 西安科技大学 Preparation method of gadolinium-doped bismuth titanate with nano-sheet cluster structure
CN110479265A (en) * 2019-07-23 2019-11-22 中国计量大学 A kind of preparation method of rare earth mixing with nano piezoelectricity catalyst

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105271380A (en) * 2015-10-31 2016-01-27 西安科技大学 Preparation method of gadolinium-doped bismuth titanate with nano-sheet cluster structure
CN110479265A (en) * 2019-07-23 2019-11-22 中国计量大学 A kind of preparation method of rare earth mixing with nano piezoelectricity catalyst

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Open date: 20100707