CN107311649A - A kind of bismuth-sodium titanate strontium titanates sub-micrometer rod and its preparation method and application - Google Patents

A kind of bismuth-sodium titanate strontium titanates sub-micrometer rod and its preparation method and application Download PDF

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CN107311649A
CN107311649A CN201710621235.6A CN201710621235A CN107311649A CN 107311649 A CN107311649 A CN 107311649A CN 201710621235 A CN201710621235 A CN 201710621235A CN 107311649 A CN107311649 A CN 107311649A
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bismuth
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sodium titanate
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CN107311649B (en
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张斗
周学凡
罗行
吴忠
周科朝
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Central South University
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    • C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
    • C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
    • C04B35/465—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates
    • C04B35/47—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on strontium titanates
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Abstract

The invention discloses the composite piezoelectric ferroelectric material of bismuth-sodium titanate strontium titanates, in polycrystalline sub-micrometer rod pattern.Present invention also offers the preparation method of described composite, including step (1)：Using sodium source A and titanium dioxide as reactant, by Na2Ti6O13Stoichiometric proportion weigh and mixed with fused salt；Mixed material is sintered at 1000~1100 DEG C again；Obtain sodium titanate monocrystalline sub-micrometer rod；Step (2)：Using titanium dioxide, sodium source B, bismuth source, barium source and sodium titanate monocrystalline sub-micrometer rod as reactant, by chemical formula Na0.5Bi0.5TiO3‑xSrTiO3Stoichiometric proportion is weighed and mixed with fused salt；Mixed material is sintered at 850~950 DEG C again, and sintered product is scrubbed, dry, and produces.Originally sodium titanate monocrystalline sub-micrometer rod, as presoma, in conjunction with the control of each key parameter of two sections of follow-up molten-salt growth methods, passes through topology reaction to the present invention；The composite piezoelectric ferroelectric material with the other bismuth-sodium titanate strontium titanates of bar-shaped submicron order can be unexpectedly made.

Description

A kind of bismuth-sodium titanate-strontium titanates sub-micrometer rod and its preparation method and application
Technical field
The present invention relates to a kind of bismuth-sodium titanate-strontium titanates sub-micrometer rod and preparation method thereof, belong to leadless piezoelectric ferroelectricity material Expect the preparation field of sub-micrometer rod.
Background technology
Piezoelectricity ferro material is as a kind of important functional material, and being suffered from fields such as electronics, machinery and communications can not The application value of replacement, using its piezoelectric property, can be prepared into various sensors, transducer and drive device etc., and utilize Its dielectric properties can then be prepared into various electric capacity and energy storage device.Conventional piezoelectricity ferro material is lead zirconate titanate at present (PZT) plumbum-based material such as, it has very excellent piezoelectricity, ferroelectricity and dielectric properties, but lead has toxicity, can harmful to human Health is simultaneously polluted, therefore need seek a kind of unleaded, environment-friendly and function admirable piezoelectricity ferro to environment Material is to replace traditional lead base piezoelectricity ferro material.In leadless piezoelectric ferroelectric material, bismuth-sodium titanate (Na0.5Bi0.5TiO3, NBT) because of its big field-induced strain with higher remanent polarization, Curie temperature, dielectric constant and discovered in recent years It is taken seriously, it is considered to be most hopeful to replace the lead-free systems of lead base piezoelectricity ferro material.
Prior art also discloses that the material and preparation method of some bismuth-sodium titanates and doping about material；For example, Publication No. CN105036736 A Chinese patent literature discloses a kind of bismuth-sodium titanate base lead-free electrostriction ceramics material, Specifically disclose a kind of technique that raw material is sintered at 800-900 DEG C, then sintered again at 1150-1200 DEG C.Publication number A kind of bismuth sodium titanate base leadless piezoelectricity material with high electric field induced strain is disclosed for CN102633503 A Chinese patent literature Material, specifically discloses a kind of technique that raw material is sintered at 800-900 DEG C in advance, is then sintered again at 1150-1250 DEG C. As can be seen that the preparation and research currently for bismuth-sodium titanate ceramic material still concentrate on and prepare broad perspectives using solid sintering technology The excellent ceramic block of energy.Such a preparation technology generally requires multiple ball milling and high-temperature sintering process, and energy consumption is larger, and prepared Ceramics be macro-size.However, as electronic component gradually moves towards miniaturization, integrated and multifunction, micro-nano size , the piezoelectricity ferro material of especially unidimensional scale is increasingly taken seriously, such as nano wire, nanometer rods, nanotube and sub-micron Rod etc., is widely studied and applied in the devices such as advanced sensors, transducer, nano generator and high energy capacitor.In nothing In lead system, compared to barium titanate (BaTiO3), the preparation and research of one-dimensional NBT bases piezoelectricity ferro material are less.
For example, the A of Publication No. CN 105860376 Chinese patent literature discloses a kind of based on NBT monocrystal nanowires Dielectric composite material preparation method, by hydro-thermal method prepare draw ratio be 20-50 NBT nanometer monocrystalline wire materials, It is combined again with vinylidene fluoride-hexafluoropropylene copolymer after it is chemically modified with dopamine, obtains dielectric composite material.Should BNT nano wires are made by hydro-thermal reaction in method.
At present, it yet there are no the relevant report that bismuth-sodium titanate-strontium titanates is combined sub-micrometer rod.
The content of the invention
It is an advantage of the invention to provide a kind of bismuth-sodium titanate of submicron-scale-strontium titanates composite piezoelectric ferroelectricity (present invention is also referred to as Na to material0.5Bi0.5TiO3-xSrTiO3, it is abbreviated as NBT-xST), the composite has the one-dimensional of uniqueness Rod-like shape.
The second object of the present invention is, it is desirable to provide a kind of preparation method that described Rod-like shape is made.
It is a third object of the invention to provide a kind of application of described bismuth-sodium titanate-strontium titanates composite.
The fourth object of the present invention is that there is provided a kind of preparation method of NBT sub-micrometer rods.
A kind of composite piezoelectric ferroelectric material of bismuth-sodium titanate-strontium titanates, in polycrystalline sub-micrometer rod pattern.
Composite piezoelectric ferroelectric material of the present invention, with one-dimensional rod-like structure；Compared to zero-dimension structural, one-dimensional rod-like Structure is more beneficial for preparing the electronic device such as high-performance sensors and high energy capacitor.
Preferably, the chemical formula Na of described composite piezoelectric ferroelectric material0.5Bi0.5TiO3-xSrTiO3, wherein, 0 ＜ x ≤0.26。
Most preferably x=0.26, now NBT-xST be located at quasi- homotype phase boundary at, can obtain maximum field-induced strain.
In the present invention, the width of described polycrystalline sub-micrometer rod or a diameter of 500nm~1 μm, length are 5~10 μm.This The described composite piezoelectric ferroelectric material of invention, with larger draw ratio.
Present invention also offers a kind of system of the composite piezoelectric ferroelectric material of bismuth-sodium titanate-strontium titanates of the special appearance Preparation Method；The present inventor attempts to prepare the composite with special Rod-like shape by template of sodium titanate；However, being opened in technology During hair, it is difficult to the material for possessing sub-micron Rod-like shape is made.The present inventor is had found finally by numerous studies, is used Two sections of molten salt method for synthesizing, coordinate the control to sintering temperature, and can unexpectedly stablize to be made has special Rod-like shape Bismuth-sodium titanate-strontium titanates composite piezoelectric ferroelectric material.
The preparation method of the composite piezoelectric ferroelectric material of bismuth-sodium titanate-strontium titanates of the present invention, comprises the following steps：
Step (1)：With sodium source A and the reactant of titanium dioxide, by Na2Ti6O13Stoichiometric proportion weigh and and fused salt Mixing；Mixed material is sintered at 1000~1100 DEG C again；Sintered product it is scrubbed, dry sodium titanate monocrystalline sub-micron Rod；
Step (2)：Using titanium dioxide, sodium source B, bismuth source, barium source and sodium titanate monocrystalline sub-micrometer rod as reactant, by chemistry Formula Na0.5Bi0.5TiO3-xSrTiO3Stoichiometric proportion is weighed and mixed with fused salt；Mixed material is again at 850~950 DEG C Sintering, sintered product is scrubbed, dry, and produces.
The present invention is originally used as forerunner using sodium titanate monocrystalline sub-micrometer rod made from one section of molten-salt growth method (step (1)) Body, in conjunction with the control of each key parameter of follow-up two sections of molten-salt growth methods (step (2)), passes through topology reaction；Can be unexpected The composite piezoelectric ferroelectric material with the other bismuth-sodium titanate-strontium titanates of bar-shaped submicron order is made in ground.
The inventive method is simple to operate, cost is low, suitable for preparing above-mentioned NBT-xST polycrystalline sub-micrometer rod on a large scale.
In the present invention, described sodium source A is the oxide of sodium or the compound of sodium；The compound of described sodium is burnt described The oxide of sodium can be changed under junction temperature.
In the present invention, described sodium source A is preferably that the carbonic acid of na oxide can be changed under the sintering temperature of step (1) Salt and/or bicarbonate；Preferably, sodium source A is sodium carbonate.
In step (1), described fused salt is less than described sintering temperature and Undec at described temperature for fusing point Stable salts.
Preferably, described fused salt is sodium chloride.
In the present invention, by described Na2Ti6O13Stoichiometric proportion weigh reactant (sodium source A and titanium dioxide), then and Fused salt is mixed.
Preferably, in step (1), quality sum and the fused salt mass ratio of reactant are 1: 1.5~2.5；It is further excellent Elect 1: 2 as.
The hybrid mode of each material refers to existing method.
Preferably, in step (1), the hybrid mode of reactant and fused salt mixes for wet ball grinding.
Preferably, the medium that wet ball grinding mixed process is used is absolute ethyl alcohol.
In step (1), it will be dried after described reaction raw materials, fused salt and medium ball milling mixing using existing method；Will be dry Material after dry is warming up at described temperature and is sintered again.
The present inventor's research is found, when preparing sodium titanate template, less than described sintering temperature, it is difficult to form sodium titanate thing Phase, and obtained material is difficult to continue the reaction of step (2), it is difficult to bar-shaped composite of the presently claimed invention is made；In addition, Temperature is higher than described higher limit, and the sodium titanate of synthesis is excessively thick, is equally unfavorable for the preparation of subsequent material.
Preferably, the heating rate of step (1) is 3~8 DEG C/min, more preferably 5 DEG C/min.
Surface is studied, in described heating rate, obtained template form is good, more conducively follow-up topology reaction, and then The composite with good Rod-like shape is more conducively made.
Preferably, in step (1), the time of sintering is 1~3 hour.
In the present invention, under the collaboration of the preferred sintering temperature, heating rate and sintering time, follow-up rod is more conducive to The preparation of shape material.
Most preferably, in step (1), sintering temperature is 1050 DEG C, and sintering time is 2 hours.
In step (1), the atmosphere of sintering reaction process is preferably air atmosphere.
In step (1), the product of sintering is soaked with deionized water, washed, through drying process after, that is, institute is made The sodium titanate monocrystalline sub-micrometer rod stated.
Na prepared by step (1)2Ti6O13The width (or diameter) of monocrystalline sub-micrometer rod is 500nm~1 μm, length 5~10 μm。
The inventors discovered that, it is more conducive to be prepared into using sodium titanate monocrystalline sub-micrometer rod made from step (1) molten-salt growth method To the composite piezoelectric ferroelectric material that pattern and performance are more excellent.
In the present invention, described sodium source B is the oxide of sodium or the compound of sodium；The compound of described sodium is burnt described The oxide of sodium can be changed under junction temperature.
In the present invention, described sodium source B is preferably that the carbonic acid of na oxide can be changed under the sintering temperature of step (1) Salt and/or bicarbonate；More preferably sodium carbonate.
Preferably, bismuth source is the oxide of bismuth or the chemical combination of the oxide of the bismuth is changed under the sintering temperature Thing.
Further preferably, described bismuth source is bismuth oxide (Bi2O3)。
Preferably, barium source is the oxide of strontium or the chemical combination of the oxide of the strontium is changed under the sintering temperature Thing.
Further preferably, barium source is strontium carbonate.
In the present invention, by described Na0.5Bi0.5TiO3-xSrTiO3Stoichiometric reaction thing (sodium source B and titanium dioxide Titanium, sodium titanate monocrystalline sub-micrometer rod, bismuth source and barium source) weigh, then mixed with fused salt.
Preferably, in step (2), described fused salt is fusing point less than described sintering temperature and at described temperature Undec stable salts.
Preferably, described fused salt is sodium chloride.
Preferably, in step (2), quality sum and the fused salt mass ratio of reactant are 1: 1.5~2.5；It is further excellent Elect 1: 2 as.
The hybrid mode of each material refers to existing method.
Preferably, in step (2), the hybrid mode of reactant and fused salt mixes for magnetic agitation.
The present inventors have additionally discovered that, in step (2), described hybrid mode is stirred using wet magnetic force, helps to maintain mould Plate shape looks, and then help that the NBT-xST with good bar-shaped sub-micron pattern is made.
Preferably, the medium that wet magnetic force stirring mixed process is used is absolute ethyl alcohol.
In step (2), dried after described reaction raw materials, fused salt and medium magnetic agitation are mixed using existing method； Dried material is warming up at described temperature again and is sintered.
The inventors discovered that, by the use of material made from step (1) as presoma, in the material proportion described in step (2) Under, at described temperature and sintering time, by topology reaction, can unexpectedly be made has bar-shaped submicrometer structure Composite piezoelectric ferroelectric material.
The present inventor's research finds, the sintering temperature of step (2) is big to the pattern of material, performance impact；The present inventor is led to Numerous studies discovery is crossed, under the template of step (1), under synthesis temperature provided by the present invention, can stablize to be made has The composite of sub-micrometer rod.
The sintering temperature of step (2) is more preferably 900~950 DEG C；Most preferably 900 DEG C.
Preferably, the heating rate of step (2) is 3~8 DEG C/min, more preferably 5 DEG C/min.
The present inventor research find, under described sintering heating rate, can be made topography uniformity more preferably, material property More excellent composite.
In the present invention, in step (2), under described sintering temperature and heating rate collaboration, sintering time preferably For 1~3 hour.
Most preferably, in step (2), the time of sintering is 2 hours.
NBT-xST sub-micrometer rods of the present invention and preparation method thereof, are prepared first with first step molten-salt growth method Na2Ti6O13Monocrystalline sub-micrometer rod, its width (or diameter) is 500nm~1 μm, 5~10 μm of length.In second step molten-salt growth method, Using above-mentioned Na2Ti6O13 monocrystalline sub-micrometer rod as presoma, NBT-xST polycrystalline sub-micron is prepared by topochemical reaction Rod, its width (or diameter) is that 500nm~1 μm, length are 5~10 μm.
The preferred method for preparing NBT-xST polycrystalline sub-micrometer rods of the invention, comprises the following steps：
Step (1)：First step molten-salt growth method prepares Na2Ti6O13Monocrystalline sub-micrometer rod：
By chemical general formula Na2Ti6O13Stoichiometric proportion weigh sodium carbonate (Na2CO3) and titanium dioxide (TiO2) powder； It is well mixed again with fused salt chlorimation sodium (NaCl) powder wet ball-milling, after drying, mixed-powder is placed in alumina crucible, with 3 ~8 DEG C/min heating rate is warming up under 1000~1100 DEG C of high temperature, is incubated 1~3 hour, and products therefrom is dried through washing, Produce；
The medium that wet ball-milling is used is absolute ethyl alcohol；
Step (2)：Second step molten-salt growth method prepares NBT-xST (0 ＜ x≤0.26) polycrystalline sub-micrometer rod：
According to chemical general formula Na0.5Bi0.5TiO3-xSrTiO3Stoichiometric proportion weigh raw material,
By Na2Ti6O13Sub-micrometer rod weighs corresponding TiO as presoma2、Na2CO3, bismuth oxide (Bi2O3) and carbon Sour strontium (SrCO3) powder is uniformly mixed with fused salt NaCl powder wet magnetic forces, after drying, mixed-powder is placed in aluminum oxide earthenware In crucible, it is warming up to 3~8 DEG C/min heating rate under 850~950 DEG C of high temperature, is incubated 1~6 hour (preferably 1~3h), institute Product is obtained through washing, drying is produced；
The medium that wet magnetic force stirring is used is absolute ethyl alcohol.
Further preferably, in step (1), sodium carbonate (Na2CO3) and titanium dioxide quality sum and fused salt NaCl matter The ratio of amount is 1: 2.
Further preferably, in step (2), most preferably soaking time is 2h.
In step (2), chemical equation is as follows：
Raw material proportioning reaction equation during X=0.1：
0.90{Na2Ti6O13+0.5Na2CO3+1.5Bi2O3}+0.6{SrCO3+TiO2}→
6{0.90Na0.5Bi0.5TiO3-0.10SrTiO3}+1.05CO2
Equation (1)
Raw material proportioning reaction equation during X=0.26：
0.74{Na2Ti6O13+0.5Na2CO3+1.5Bi2O3}+1.56{SrCO3+TiO2}→6{0.74Na0.5Bi0.5TiO3- 0.26SrTiO3}+1.93CO2
Equation (2)
The present invention also includes a kind of preparation method of bar-shaped NBT sub-micrometer rods, preparation process and NBT-xST sub-micron Rod is identical, and difference is in second of fused salt sintering process, and x is equal to 0.
It is preferred that bismuth-sodium titanate sub-micrometer rod preparation method, comprise the following steps：
Step (a)：With sodium carbonate and the reactant of titanium dioxide, by Na2Ti6O13Stoichiometric proportion weigh and and fused salt Mixing；Mixed material is sintered at 1000~1100 DEG C again；Sintered product it is scrubbed, dry sodium titanate monocrystalline sub-micron Rod；
Step (b)：Using titanium dioxide, sodium carbonate, bismuth oxide and sodium titanate monocrystalline sub-micrometer rod as reactant, by chemical formula Na0.5Bi0.5TiO3Stoichiometric proportion is weighed and mixed with fused salt；Sintering 1~6 is small at 850~950 DEG C again for mixed material When, sintered product is scrubbed, dry, and produces.
The preparation method of NBT sub-micrometer rods still more preferably, comprises the following steps：
Step (a)：First step molten-salt growth method prepares Na2Ti6O13Monocrystalline sub-micrometer rod：
By chemical general formula Na2Ti6O13Stoichiometric proportion weigh sodium carbonate (Na2CO3) and titanium dioxide (TiO2) powder； It is well mixed again with fused salt chlorimation sodium (NaCl) powder wet ball-milling, after drying, mixed-powder is placed in alumina crucible, with 3 ~8 DEG C/min heating rate is warming up under 1000~1100 DEG C of high temperature, is incubated 1~3 hour, and products therefrom is dried through washing, Produce；
The medium that wet ball-milling is used is absolute ethyl alcohol；
Step (b)：Second step molten-salt growth method prepares NBT sub-micrometer rods：
According to chemical general formula Na0.5Bi0.5TiO3Stoichiometric proportion weigh raw material,
By Na2Ti6O13Sub-micrometer rod weighs corresponding TiO as presoma2、Na2CO3And bismuth oxide (Bi2O3) with melting Salt NaCl powder wet magnetic forces are uniformly mixed, and after drying, mixed-powder is placed in alumina crucible, with 3~8 DEG C/min's Heating rate is warming up under 850~950 DEG C of high temperature, is incubated 6 hours, and products therefrom is produced through washing, drying；
The medium that wet magnetic force stirring is used is absolute ethyl alcohol.
Described NBT sub-micrometer rods are prepared shown in equation such as equation (3)：
{Na2Ti6O13+0.5Na2CO3+1.5Bi2O3}→6{Na0.5Bi0.5TiO3}+0.5CO2
Equation (3)
Present invention also offers a kind of application of described composite piezoelectric ferroelectric material, applied to prepare advanced sensors, Transducer, nano generator, high energy capacitor device.
Beneficial effects of the present invention：
(1) present invention firstly provides preparing bar-shaped NBT-xST sub-micrometer rods, and with unexpected piezoelectricity ferro Energy.
(2) NBT, NBT-0.10ST polycrystalline sub-micrometer rod show butterfly-like amplitude-voltage curve, and maximum piezoelectric response is shaken Width reaches 1.6nm；And NBT-0.26ST polycrystalline sub-micrometer rods show bean sprouts shape amplitude-voltage curve, maximum piezoelectric response amplitude Up to 2.3nm.
(3) it has also been found that, under the described operation of two step fused salt preparation process and the control of parameter, people can be gone out The Rod-like shape material with excellent properties is made with expecting, and the preparation method is simple to operate, cost is low, suitable for extensive Prepare.
(4) the NBT-xST sub-micrometer rods that prepare of the present invention, width is that 500nm~1 μm, length are 5~10 μm, with compared with Big draw ratio.
(5) NBT-xST sub-micrometer rods prepared by the present invention, with the change of x values, sub-micrometer rod shows different ferroelectricities Characteristic, can be widely used in fields such as MEMS, nano generator and energy stores.
Brief description of the drawings
Fig. 1：(a), (b), (c), (d) are respectively Na prepared by embodiment 12Ti6O13Monocrystalline sub-micrometer rod, embodiment 2 are made NBT polycrystalline sub-micrometer rod, NBT- made from NBT-0.10ST polycrystalline sub-micrometer rod made from embodiment 3 and embodiment 4 The XRD testing results of 0.26ST polycrystalline sub-micrometer rods.
Fig. 2：(a), (b), (c), (d) are respectively Na prepared by embodiment 12Ti6O13Monocrystalline sub-micrometer rod, embodiment 2 are made NBT polycrystalline sub-micrometer rod, NBT- made from NBT-0.10ST polycrystalline sub-micrometer rod made from embodiment 3 and embodiment 4 The ESEM testing result of 0.26ST polycrystalline sub-micrometer rods.
Fig. 3：The HAADF images of the NBT-0.26ST polycrystalline sub-micrometer rods prepared described in embodiment 4 and Elemental redistribution face Sweep figure.
Fig. 4：(a), (b), (c) be respectively embodiment 2, embodiment 3, NBT, NBT-0.10ST for preparing described in embodiment 4 Returned with the piezoelectric forces Microscopy Results of NBT-0.26ST polycrystalline sub-micrometer rods, including amplitude-voltage curve and phase-voltage Line.
Fig. 5：The Na made from embodiment 52Ti6O13The SEM figures of monocrystalline sub-micrometer rod；
Fig. 6：The Na made from embodiment 62Ti6O13The SEM figures of monocrystalline sub-micrometer rod；
Fig. 7：The SEM figures of the NBT-0.26ST polycrystalline sub-micrometer rod made from embodiment 7；
Fig. 8：The SEM figures of the NBT-0.26ST polycrystalline sub-micrometer rod made from embodiment 8；
Fig. 9：The Na made from comparative example 12Ti6O13SEM figure；
Figure 10：The Na made from comparative example 22Ti6O13SEM figure；
Figure 11：The SEM figures of the NBT-0.26ST polycrystalline sub-micrometer rod made from comparative example 3；
Figure 12：The SEM figures of the NBT-0.26ST polycrystalline sub-micrometer rod made from comparative example 4.
Fig. 1 can be seen that the product of all preparations is pure phase, not contain any impurity.Prepared NBT, NBT- 0.10ST, NBT-0.26ST have been respectively formed uniform solid solution.
Fig. 2 can be seen that prepared Na2Ti6O13For monocrystalline sub-micrometer rod structure, width is 500nm~1 μm, length is about 10μm.Prepared NBT-xST is polycrystalline sub-micrometer rod structure, and width is that 500nm~1 μm, length are 5~10 μm, with larger Draw ratio.
Fig. 3 can be seen that 5 kinds of elements Srs2+, Bi3+, Na+, Ti4+, O2-It is evenly distributed in whisker, illustrates prepared NBT-0.26ST polycrystalline sub-micrometer rod is uniform solid solution structure.
Fig. 4 can be seen that NBT, NBT-0.10ST polycrystalline sub-micrometer rod and show butterfly-like amplitude-voltage curve, maximum Piezoelectric response amplitude reaches 1.6nm；And NBT-0.26ST polycrystalline sub-micrometer rods show bean sprouts shape amplitude-voltage curve, maximum pressure Electroresponse amplitude reaches 2.3nm.Meanwhile, compared with NBT, NBT-0.10ST polycrystalline sub-micrometer rod, NBT-0.26ST polycrystalline sub-micron Amplitude-the voltage curve and phase of rod-voltage loop line all show the hysteresis that may be significantly smaller.As a result prove prepared NBT, NBT-0.10ST polycrystalline sub-micrometer rod is normal frroelectrics, and prepared NBT-0.26ST polycrystalline sub-micrometer rod is relaxor ferroelectric Body.Its different ferroelectric properties makes it have different applications in fields such as MEMS, nano generator and energy stores Value.
Specific embodiment
Embodiment 1
First step molten-salt growth method prepares Na2Ti6O13Monocrystalline sub-micrometer rod：
Weigh 2.650g Na2CO3Powder, 11.975g TiO2Powder and 29.250g NaCl powder, are made with absolute ethyl alcohol For medium, wet ball-milling 24h after uniform mixing, is dried, is sieved powder, mixed powder is placed in alumina crucible, with 5 DEG C/min Heating rate rise to 1050 DEG C (sintering temperatures), be incubated 2 hours, after soaking time terminates, naturally cool to room temperature.It will obtain Product deionized water soak, suction filtration, cleaning, be dried to obtain Na in the drying box for placing into 80 DEG C2Ti6O13Monocrystalline sub-micron Rod.
Embodiment 2
Second step molten-salt growth method prepares NBT polycrystalline sub-micrometer rods：
Weigh 2.710g Na2Ti6O13Monocrystalline sub-micrometer rod (embodiment 1 is made), 0.265g Na2CO3Powder, 3.495g Bi2O3Powder and 12.940g NaCl powder, using absolute ethyl alcohol as medium, magnetic agitation 6h after uniform mixing, is dried, sieve Powder, mixed powder is placed in alumina crucible, and 900 DEG C are risen to 5 DEG C/min heating rate, is incubated 6 hours, soaking time After end, room temperature is naturally cooled to.Obtained product deionized water is soaked, suction filtration, cleaning, place into 80 DEG C of drying box In be dried to obtain NBT polycrystalline sub-micrometer rods.
Embodiment 3
Second step molten-salt growth method prepares NBT-0.10ST polycrystalline sub-micrometer rods：
Weigh 2.435g Na2Ti6O13Monocrystalline sub-micrometer rod (embodiment 1 is made), 0.239g Na2CO3Powder, 3.145g Bi2O3Powder, 0.443g SrCO3Powder, 0.240g TiO2Powder and 13.003gNaCl powder, Jie is used as using absolute ethyl alcohol Matter, magnetic agitation 6h after uniform mixing, is dried, is sieved powder, mixed powder is placed in alumina crucible, with 5 DEG C/min heating Speed rises to 900 DEG C, is incubated 2 hours, after soaking time terminates, naturally cools to room temperature.By obtained product deionized water NBT-0.10ST polycrystalline sub-micrometer rods are dried to obtain in immersion, suction filtration, cleaning, the drying box for placing into 80 DEG C.
Embodiment 4
Second step molten-salt growth method prepares NBT-0.26ST polycrystalline sub-micrometer rods：
Weigh 2.018g Na2Ti6O13Monocrystalline sub-micrometer rod (embodiment 1 is made), 0.196g Na2CO3Powder, 2.586g Bi2O3Powder, 1.152SrCO3Powder, 0.623g TiO2Powder and 13.150gNaCl powder, using absolute ethyl alcohol as medium, Magnetic agitation 6h, after uniform mixing, dries, sieves powder, mixed powder is placed in alumina crucible, with 5 DEG C/min heating speed Rate rises to 900 DEG C (sintering temperatures), is incubated 2 hours, after soaking time terminates, naturally cools to room temperature.Obtained product is used NBT-0.26ST polycrystalline sub-micrometer rods are dried to obtain in deionized water immersion, suction filtration, cleaning, the drying box for placing into 80 DEG C.
Embodiment 5
Compare, differ only in embodiment 1, sintering temperature is 1000 DEG C.Obtain Na2Ti6O13Monocrystalline sub-micrometer rod.This The SEM figures of material made from embodiment are shown in Fig. 5.Width is 500nm~1 μm, length is about 10 μm.
Embodiment 6
Compare, differ only in embodiment 1, sintering temperature is 1100 DEG C.Obtain Na2Ti6O13Monocrystalline sub-micrometer rod.This The SEM figures of material made from embodiment are shown in Fig. 6.Width is 500nm~1 μm, length is about 10 μm.
Embodiment 7
Compare, differ only in embodiment 4, in second step crystal growth from flux NBT-0.26ST polycrystalline sub-micrometer rods, burn Junction temperature is 850 DEG C.Obtained material is in sub-micrometer rod；SEM figures are shown in Fig. 7.
Embodiment 8
Compare, differ only in embodiment 4, in second step crystal growth from flux NBT-0.26ST polycrystalline sub-micrometer rods, burn Junction temperature is 950 DEG C.Obtained material is in sub-micrometer rod；SEM figures are shown in Fig. 8.
Comparative example 1
Compare, differ only in embodiment 1, sintering temperature is 900 DEG C.The SEM figures of material made from this comparative example are shown in Fig. 9.As shown in Figure 9, obtained Na2Ti6O13Size is smaller, and in second step fused salt process, Rod-like shape is easily damaged, it is difficult to Maintain.
Comparative example 2
Compare, differ only in embodiment 1, in first step crystal growth from flux Na2Ti6O13 monocrystalline sub-micrometer rods, sintering Temperature is 1150 DEG C, is incubated 2 hours, obtained Na2Ti6O13SEM figures see Figure 10；As shown in Figure 10, Na2Ti6O13It is very thick Greatly, size is uneven and draw ratio is small.
Comparative example 3
Compared with embodiment 4, difference is, in second step crystal growth from flux NBT-0.26ST polycrystalline sub-micrometer rods, sintering Temperature is 800 DEG C.The SEM figures of material made from this comparative example are shown in Figure 11, a small amount of surface are still suffered from as seen from the figure, in product smooth Monocrystalline sub-micrometer rod, be unreacted Na2Ti6O13, it was demonstrated that temperature is too low, it is impossible to carry out second step reaction complete.
Comparative example 4
Compared with embodiment 4, difference is, in second step crystal growth from flux NBT-0.26ST polycrystalline sub-micrometer rods, sintering Temperature is 1000 DEG C.The SEM figures of obtained NBT-0.26ST materials are shown in Figure 12；As shown in Figure 12, it is impossible to be maintained club shaped structure. Ferroelectricity/piezoelectric property data are significantly worse than material made from embodiment.

Claims (10)

1. a kind of composite piezoelectric ferroelectric material of bismuth-sodium titanate-strontium titanates, it is characterised in that in polycrystalline sub-micrometer rod pattern；
The width or diameter of polycrystalline sub-micrometer rod are preferably that 500nm~1 μm, length are preferably 5~10 μm.
2. the composite piezoelectric ferroelectric material of bismuth-sodium titanate-strontium titanates as claimed in claim 1, it is characterised in that described answers The chemical formula Na of combined pressure ferroelectric electric material0.5Bi0.5TiO3-xSrTiO3, wherein, 0 ＜ x≤0.26.
3. the preparation method of the composite piezoelectric ferroelectric material of bismuth-sodium titanate-strontium titanates as claimed in claim 1 or 2, its feature It is, comprises the following steps：
Step (1)：Using sodium source A and titanium dioxide as reactant, by Na2Ti6O13Stoichiometric proportion weigh and mixed with fused salt； Mixed material is sintered at 1000~1100 DEG C again；Sintered product it is scrubbed, dry sodium titanate monocrystalline sub-micrometer rod；
Step (2)：Using titanium dioxide, sodium source B, bismuth source, barium source and sodium titanate monocrystalline sub-micrometer rod as reactant, by chemical formula Na0.5Bi0.5TiO3-xSrTiO3Stoichiometric proportion is weighed and mixed with fused salt；Mixed material burns at 850~950 DEG C again Knot, sintered product is scrubbed, dry, and produces.
4. the preparation method of the composite piezoelectric ferroelectric material of bismuth-sodium titanate-strontium titanates as claimed in claim 3, its feature exists In described sodium source A and sodium source B are the oxide of sodium or the compound of sodium alone；The compound of described sodium is in the sintering At a temperature of can change into the oxide of sodium；Preferably sodium carbonate；
Bismuth source is the oxide of bismuth, or changes under the sintering temperature compound of the oxide of the bismuth；Preferably oxygen Change bismuth；
Barium source is the oxide of strontium, or changes under the sintering temperature compound of the oxide of the strontium；Preferably carbon Sour strontium；
Described Na2Ti6O13Monocrystalline sub-micrometer rod width or a diameter of 500nm~1 μm, length are 5~10 μm.
5. the preparation method of the composite piezoelectric ferroelectric material of bismuth-sodium titanate-strontium titanates as described in claim 3 or 4, its feature It is, in step (1), the time of sintering is 1~3 hour；
In step (2), sintering time preferably is 1~6 hour；More preferably 1~3 hour.
6. the preparation method of the composite piezoelectric ferroelectric material of bismuth-sodium titanate-strontium titanates as described in claim 3 or 4, its feature It is, the heating rate of step (1) and step (2) is 3~8 DEG C/min.
7. the preparation method of the composite piezoelectric ferroelectric material of bismuth-sodium titanate-strontium titanates as claimed in claim 3, its feature exists In the wet ball grinding that is mixed into described in step (1) is mixed；The medium that wet ball grinding mixed process is used is absolute ethyl alcohol；
Wet magnetic force stirring is mixed into described in step (2), the medium that wet magnetic force stirring mixed process is used is absolute ethyl alcohol.
8. the preparation method of the composite piezoelectric ferroelectric material of bismuth-sodium titanate-strontium titanates as claimed in claim 3, its feature exists In described fused salt is sodium chloride；In step (1) and step (2), the quality of reactant and fused salt mass ratio be 1: 1.5~ 2.5。
9. any one of composite piezoelectric ferroelectric material or claim 3~8 described in a kind of any one of claim 1~2 system The application of the composite piezoelectric ferroelectric material of Preparation Method, it is characterised in that sent out applied to advanced sensors, transducer, nanometer is prepared Motor, high energy capacitor device.
10. a kind of preparation method of bismuth-sodium titanate sub-micrometer rod, it is characterised in that comprise the following steps：
Step (a)：Using sodium carbonate and titanium dioxide as reactant, by Na2Ti6O13Stoichiometric proportion weigh and mixed with fused salt； Mixed material is sintered at 1000~1100 DEG C again；Sintered product it is scrubbed, dry sodium titanate monocrystalline sub-micrometer rod；
Step (b)：Using titanium dioxide, sodium carbonate, bismuth oxide, strontium carbonate and sodium titanate monocrystalline sub-micrometer rod as reactant, by change Formula Na0.5Bi0.5TiO3Stoichiometric proportion is weighed and mixed with fused salt；Mixed material sinters 1 at 850~950 DEG C again ~6 hours, sintered product was scrubbed, dry, and produces.
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108623302A (en) * 2018-06-26 2018-10-09 桂林电子科技大学 A kind of leadless piezoelectric nano-array and preparation method thereof
CN109928422A (en) * 2018-08-14 2019-06-25 华北理工大学 A kind of method that fused salt prepares potassium titanate crystal
CN110948981A (en) * 2019-12-05 2020-04-03 陕西科技大学 PVDF (polyvinylidene fluoride) high-energy-density composite film material with sandwich structure and preparation method thereof
CN113459542A (en) * 2021-06-28 2021-10-01 陕西科技大学 PVDF (polyvinylidene fluoride) -based composite film with double-layer structure and preparation method thereof
CN114873636A (en) * 2022-06-16 2022-08-09 西安交通大学 Lead titanate substrate crystal template and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101220511A (en) * 2007-09-30 2008-07-16 中国科学院上海硅酸盐研究所 Method for manufacturing bismuth sodium titanate-barium titanate ferro-electricity single crystal
CN102815939A (en) * 2012-07-16 2012-12-12 同济大学 Leadless piezoelectric textured ceramic material and preparation method thereof
US20140239774A1 (en) * 2012-12-17 2014-08-28 Virginia Tech Intellectual Properties, Inc. NEW PROCESSING METHOD FOR GRAIN-ORIENTED LEAD-FREE PIEZOELECTRIC Na0.5Bi0.5TiO3-BaTiO3 CERAMICS EXHIBITING GIANT PERFORMANCE

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101220511A (en) * 2007-09-30 2008-07-16 中国科学院上海硅酸盐研究所 Method for manufacturing bismuth sodium titanate-barium titanate ferro-electricity single crystal
CN102815939A (en) * 2012-07-16 2012-12-12 同济大学 Leadless piezoelectric textured ceramic material and preparation method thereof
US20140239774A1 (en) * 2012-12-17 2014-08-28 Virginia Tech Intellectual Properties, Inc. NEW PROCESSING METHOD FOR GRAIN-ORIENTED LEAD-FREE PIEZOELECTRIC Na0.5Bi0.5TiO3-BaTiO3 CERAMICS EXHIBITING GIANT PERFORMANCE

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
郑凯平: "(0.84-x) Na0.5Bi0.5TiO3 -0.16K0.5Bi0.5TiO3 － xSrTiO系无铅压电陶瓷结构与电性能", 《功能材料》 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108623302A (en) * 2018-06-26 2018-10-09 桂林电子科技大学 A kind of leadless piezoelectric nano-array and preparation method thereof
CN108623302B (en) * 2018-06-26 2021-01-05 桂林电子科技大学 Lead-free piezoelectric nano array and preparation method thereof
CN109928422A (en) * 2018-08-14 2019-06-25 华北理工大学 A kind of method that fused salt prepares potassium titanate crystal
CN110948981A (en) * 2019-12-05 2020-04-03 陕西科技大学 PVDF (polyvinylidene fluoride) high-energy-density composite film material with sandwich structure and preparation method thereof
CN110948981B (en) * 2019-12-05 2022-06-24 陕西科技大学 PVDF (polyvinylidene fluoride) high-energy-density composite film material with sandwich structure and preparation method thereof
CN113459542A (en) * 2021-06-28 2021-10-01 陕西科技大学 PVDF (polyvinylidene fluoride) -based composite film with double-layer structure and preparation method thereof
CN114873636A (en) * 2022-06-16 2022-08-09 西安交通大学 Lead titanate substrate crystal template and preparation method thereof
CN114873636B (en) * 2022-06-16 2023-03-10 西安交通大学 Lead titanate substrate crystal template and preparation method thereof

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