CN102443852A - Manganese-doped sodium bismuth titanate-barium titanate lead-free piezoelectric single crystal and preparation method thereof - Google Patents
Manganese-doped sodium bismuth titanate-barium titanate lead-free piezoelectric single crystal and preparation method thereof Download PDFInfo
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- CN102443852A CN102443852A CN201010299222XA CN201010299222A CN102443852A CN 102443852 A CN102443852 A CN 102443852A CN 201010299222X A CN201010299222X A CN 201010299222XA CN 201010299222 A CN201010299222 A CN 201010299222A CN 102443852 A CN102443852 A CN 102443852A
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Abstract
The invention belongs to the field of crystal growth and relates to a manganese-doped sodium bismuth titanate-barium titanate lead-free piezoelectric single crystal and a preparation method thereof. The chemical components of the manganese-doped sodium bismuth titanate-barium titanate lead-free piezoelectric single crystal meet the following chemical composition formula: (1-x)Na[0.5]Bi[0.5]TiO[3]-xBaTiO[3]-yat%Mn, wherein x is more than 0 and less than 1.0, y is larger than or equal to 0.1 and less than or equal to 0.4, yat% represents the molar percentage of Mn accounting for (1-x)Na[0.5]Bi[0.5]TiO[3]-xBaTiO[3]. In the invention, the Mn-doped NBBT (sodium bismuth titanate-barium titanate) lead-free piezoelectric single crystal is grown by adopting a top seed crystal flux pulling technique, the piezoelectric constant d33 of the single crystal reaches 500pC/N, and the electromechanical coupling coefficient kt reaches 60%, thus the manganese-doped sodium bismuth titanate-barium titanate lead-free piezoelectric single crystal reaches a use level, can be applied to the fields of high-frequency ultrasonic transducers, industrial fault detection, medicine ultrasonic projects and the like.
Description
Technical field
The invention belongs to field of crystal growth, relate to the adulterated bismuth sodium titanate-barium titanate leadless piezoelectric of a kind of manganese monocrystalline and preparation method thereof.
Background technology
Piezoelectric is an important functional material, is widely used in fields such as transverter, piezoelectric transformer, wave filter and ultrasonic motor.Piezoelectric occupies quite great proportion as important functional material in field of electronic materials.In recent years, piezoelectric was pressed about 15% speed increment at global annual sales.According to statistics, global piezoelectric product sales reached more than 3,000,000,000 dollars approximately in 2000.But studying and use the most at present, piezoelectric is PZT, PMNT and PZNT lead base composite perofskite type relaxation ferroelectric.Although these materials have very excellent electric property because plumbous content has surpassed 60% in the lead base material, make this type material produce, use and the process of discarded aftertreatment in brought serious harm for human environment and ecology.In recent years, European Union has issued a series of decree, like hazardous substance illegal instruction (ROHS instruction), limits being used on the motor electronics of lead-containing materials, and the U.S. and Japan and other countries have also been passed through similar decree in succession.Although also belong to one of exemption item of ROHS so far for piezoelectric in the electronic product, believe in the near future also can be restricted, so the research and development of leadless piezoelectric material material become the hot fields that countries in the world are concerned about.
Bismuth-sodium titanate Na
0.5Bi
0.5TiO
3(NBT) be that room temperature is a trigonal crystal structure perovskite typed ferroelectrics, (remnant polarization Pr reaches 38 μ C/cm by force to have ferroelectricity
2), characteristic such as specific inductivity is little and acoustical behavior is good, be applicable to fields such as high-frequency transducer, industrial flaw detection and medical supersonic engineering.But simultaneously, NBT base leadless piezoelectricity material also has its many weak points, and like coercive field higher (being 73kV/cm), piezoelectric property can not demonstrated fully by the restriction of polarized electric field; The depolarize temperature is low, and the use temperature scope is narrower; Mechanical quality factor is lower, is not suitable for the application in high-power field.The appearance of bismuth sodium titanate-barium titanate (NBBT) system solid solution effectively improves its piezoelectric property; Especially near accurate homotype phase boundary (MPB); But its leakage current is bigger; Polarization process is still difficult, and its due piezoelectric property can't be embodied, and the leakage current of therefore how effectively controlling in the NBBT crystal is the key point that improves the NBBT piezoelectric property.
Summary of the invention
The purpose of this invention is to provide the adulterated bismuth sodium titanate-barium titanate of a kind of manganese (NBBT) leadless piezoelectric monocrystalline (Mn:NBBT) and preparation method thereof; Be difficult to the polar problem to solve in the prior art in the NBBT crystal samples that drawback was produced such as oxygen vacancy concentration height and leakage current be bigger; The adulterated bismuth sodium titanate-barium titanate of said manganese (NBBT) leadless piezoelectric monocrystalline has effectively improved NBBT crystalline polarization process; Obviously improved NBBT crystalline piezoelectric property and electromechanical coupling performance, its performance has reached even has surpassed the level of commercial PZT pottery.
The adulterated bismuth sodium titanate-barium titanate leadless piezoelectric of a kind of manganese monocrystalline, its Chemical Composition meet chemical constitution formula (1-x) Na
0.5Bi
0.5TiO
3-xBaTiO
3-y at%Mn, 0＜x＜1,0.1≤y≤0.4 wherein, on behalf of Mn, y at% account for (1-x) Na
0.5Bi
0.5TiO
3-xBaTiO
3Molar percentage.
Preferably, 0.05≤x≤0.07, y=0.2.
Wherein, 1-x and x represent Na
0.5Bi
0.5TiO
3And BaTiO
3Mol ratio.
The preparation of the adulterated bismuth sodium titanate-barium titanate leadless piezoelectric of manganese of the present invention monocrystalline is divided into two and goes on foot greatly: the first step is the pre-treatment of crystal growth raw material; Second step was to select suitable crucible and suitable growth technique condition, with the adulterated NBBT monocrystalline of top seed crystal flux pulling technique growth Mn.
The preparation method of the adulterated bismuth sodium titanate-barium titanate leadless piezoelectric of manganese of the present invention monocrystalline may further comprise the steps:
1), according to chemical constitution formula (1-x) Na
0.5Bi
0.5TiO
3-xBaTiO
3Stoichiometric ratio weighing sodium carbonate and the bismuth oxide of middle Na and Bi; Take by weighing titanium oxide and barium carbonate respectively according to the excessive respectively 1-2 of the stoichiometric ratio of Ti and Ba in said chemical constitution formula amount doubly; Take by weighing Manganse Dioxide again, total mole the molar percentage that said Manganse Dioxide accounts for yellow soda ash, bismuth oxide, titanium oxide and barium carbonate is 1-2at%;
2), the raw material that takes by weighing is added solubility promoter: yellow soda ash and bismuth oxide, ball milling also mixes;
3), the material briquetting that mixes being obtained rising of crystal growth expects;
4), will rise to expect and put into the crucible of monocrystal growing furnace, being heated to the fusing of expecting fully, the rising to expect of insulation to fusing mixes; Adopting < 001>direction NBBT monocrystalline is that seed crystal carries out crystal growth, obtains the adulterated bismuth sodium titanate-barium titanate leadless piezoelectric of said manganese monocrystalline after the cooling, wherein; The thermograde of solid-liquid interface is 5～100 ℃/cm; The seed rod speed of rotation is 6～15rpm, and the rate of pulling is 0.5～1.5mm/day, and the rate of temperature fall in the crystal growing process is 3～5 ℃/day; Crystal growth is reduced to room temperature with the rate of temperature fall of 50～200 ℃/h after accomplishing.
Preferably, take by weighing titanium oxide and barium carbonate respectively according to the excessive respectively 1.6 times amount of the stoichiometric ratio of Ti and Ba in the said chemical constitution formula in the said step 1); Total mole the molar percentage that said Manganse Dioxide accounts for yellow soda ash, bismuth oxide, titanium oxide and barium carbonate is preferably 1at%.
Said step 2) raw material that adds in before the solubility promoter can first ball milling, puts into the crucible sintering again, then fine grinding; Wherein sintering temperature can be 1000 ℃, and sintering time can be 10h.
Material in the said step 3) before the briquetting can be put into the crucible sintering earlier, then pulverizing, fine grinding; Wherein sintering temperature can be 1000 ℃, and sintering time can be 10h.
The total mass ratio of yellow soda ash, bismuth oxide, titanium oxide and barium carbonate is (15-20) in yellow soda ash in the said solubility promoter, bismuth oxide and the raw material: (15-20): 100.
The purity of above-mentioned all raw materials is analytically pure raw material.
Said crucible is preferably platinum crucible;
Said ball milling can be wet ball-milling, and the said ball milling time is to be 20h;
The condition of said briquetting is an isostatic cool pressing.
Said monocrystal growing furnace adopts resistance heating element heating, particularly SiC or MoSi
2The rod heating; Increase logical oxygen unit at bottom of furnace body; Pulling apparatus comprises rotation and pulling apparatus.
Said seed rod rotation can adopt folk prescription to rotation.
The present invention carries out sintering through the preparatory synthesis method of solid state reaction with raw material and prepares the required polycrystal raw material of Mn doping NBBT single crystal growing, is the adulterated NBBT polycrystal raw material of the Mn of calcium titanium ore structure; After wet ball-milling mixes once more with adding fusing assistant in the preparatory synthetic polycrystal raw material; Carry out solid state reaction again; Finally obtain containing the polycrystal raw material of the Mn doping NBBT of fusing assistant, i.e. rising of crystal growth expected, and wherein the adding of solubility promoter can reduce the temperature of crystal growth.Adopting < 001>direction NBBT crystal among the preparation method of the present invention is that seed crystal is a key character of the present invention, can obtain high-quality monocrystalline by this direction growth.
The present invention is through mixing Mn in the NBBT monocrystalline; The position of Mn instead Ti has reduced the leakage current in the NBBT monocrystalline largely, has reduced the concentration in oxygen room in the NBBT crystal; Effectively improve NBBT crystalline polarization process, significantly improved NBBT crystalline piezoelectricity and electromechanical coupling performance.High-performance Mn doping with bismuth titanate sodium-its piezoelectric constant of barium titanate lead-less piezoelectric monocrystal d of the present invention's growth
33Reach 500pC/N, electromechanical coupling factor k
tReach 60%, reached usage level, can be widely used in fields such as high-frequency transducer, industrial flaw detection and medical supersonic engineering.
Description of drawings
Fig. 1 is the sectional view of top seed crystal solubility promoter crystal pulling method monocrystal growing furnace synoptic diagram.1 is porthole among the figure, and 2 is thermal insulation layer, and 3 is platinum crucible, and 4 is stool, and 5 is seed rod, and 6 is Si-Mo rod, and 7 is thermopair, and 8 is logical oxygen system in body of heater.
Fig. 2 is the adulterated NBBT crystal of Mn that adopts embodiment 1 to be grown.
Fig. 3 is the Mn doping 0.95NBT-0.05BT crystalline X-ray powder diffraction spectrum of embodiment 1 gained.
Fig. 4 is the Mn doping 0.95NBT-0.05BT crystalline specific inductivity (ε of embodiment 1 gained
r), dielectric loss (tan δ) and temperature (℃) between funtcional relationship.
Fig. 5 be the Mn doping 0.95NBT-0.05BT crystalline thickness vibration mode of embodiment 1 gained impedance (Ω), phase angle (°) and frequency (Hz) between funtcional relationship.
Fig. 6 is the temperature stability of the Mn doping 0.95NBT-0.05BT crystalline thickness electromechanical coupling coefficient of embodiment 1 gained.
Fig. 7 is the contrast of different electric Mn doping after the match NBBT with the NBBT leakage current density that do not mix of embodiment 1 gained.
Embodiment
Further set forth the present invention below in conjunction with specific embodiment, should be understood that these embodiment only are used to the present invention is described and are not used in restriction protection scope of the present invention.
Take by weighing purity and be 99.99% 70.94g yellow soda ash, 311.84g (benefit is gone into) bismuth oxide, 243.56g titanium oxide (excessive 1.6 times), 72.05g (excessive 1.6 times) barium carbonate and 2.45g Manganse Dioxide, dry back-mixing and ball milling was placed in the platinum crucible of adding a cover 1000 ℃ of thermal treatments 10 hours in 20 hours.Then with the products therefrom fine grinding, sieve, based on the total amount W of polycrystal raw material yellow soda ash, bismuth oxide, titanium oxide and barium carbonate
AlwaysAdd a certain proportion of yellow soda ash and bismuth oxide as fusing assistant, its mass ratio is Na
2CO
3: Bi
2O
3: W
AlwaysEqual 20: 20: 100, place the platinum crucible of adding a cover once more 1000 ℃ of thermal treatments 10 hours.At last with product pulverizing, fine grinding, sieve, become piece through isostatic cool pressing.To press caked raw material to pack in the platinum growth crucible, growth crucible is placed in the reactors shown in Figure 1 again.After intensification was melted raw material fully, after 30 ℃ of heat, insulation 20h made the abundant convection current of pyrosol, mixes.Make temperature slowly reduce to solution saturation point temperature, adopting < 001>direction NBBT monocrystalline is seed crystal, and the selection rate of pulling is that 1.5mm/day, rotating speed are that 15rpm carries out the NBBT crystal growth.In the crystal growing process, with the cooling of the rate of temperature fall of 5 ℃/day, and in body of heater aerating oxygen.After crystal breaks away from liquid level, stop to lift, be cooled to room temperature with the rate of temperature fall of 50 ℃/h, obtaining chemical constitution formula is 0.95Na
0.5Bi
0.5TiO
3-0.05BaTiO
3The adulterated bismuth sodium titanate-barium titanate leadless piezoelectric of the manganese of-0.2at%Mn monocrystalline.
Through detecting, the crystal that grows is as shown in Figure 2, and size can arrive Φ 35mm * 10mm; Gained crystalline X-ray powder diffraction spectrum is as shown in Figure 3, shows that the crystal of growth has pure tripartite uhligite phase structure.Gained crystalline dielectric properties are as shown in Figure 4, and the depolarize temperature is near 120 ℃.Gained crystalline thickness vibration mode impedance spectrum is as shown in Figure 5, and according to the standard of IEEE, the thickness mode electromechanical coupling factor that calculates gained reaches more than 60%.The temperature stability of thickness mode is as shown in Figure 6, and before the depolarize temperature, thickness electromechanical coupling coefficient has good temperature stability, promptly has the temperature use range of broad.Room temperature lower piezoelectric constant d
33Can reach 500pC/N.After Mn mixed, the leakage current density in the NBBT crystal obviously reduces, and was as shown in Figure 7.
Can find out that by present embodiment preparation method with top provided by the invention seed crystal flux pulling technique growth Mn doping NBBT monocrystalline can grow size and reach Φ 35mm * 10mm, piezoelectric constant d
33Reach 500pC/N, electromechanical coupling factor k
tReach 60% the unleaded monocrystalline of high tension performance.
The piezoelectric coefficient d of NBBT monocrystalline involved in the present invention
33Be the ZJ-3A type d that makes with Acoustical Inst., Chinese Academy of Sciences
33Tester is directly measured; Specific inductivity converts after with HP4192A type electric impedance analyzer measure sample electric capacity and obtains; Electromechanical coupling factor k
tMeasurement be according to the IEEE176-78 standard, measure the impedance under the different frequency with HP4294A type electric impedance analyzer after, according to formula
The wherein Δ f=f that calculates
p-f
s
Take by weighing purity and be 99.99% 70.94g yellow soda ash, 311.84g bismuth oxide, 243.56g titanium oxide (excessive 1.6 times), 72.05g barium carbonate (excessive 1.6 times) and 2.45g Manganse Dioxide, dry back-mixing and ball milling was placed in the platinum crucible of adding a cover 1000 ℃ of thermal treatments 10 hours in 20 hours.Then with the products therefrom fine grinding, sieve, based on the total amount W of polycrystal raw material yellow soda ash, bismuth oxide, titanium oxide and barium carbonate
AlwaysAdd a certain proportion of yellow soda ash and bismuth oxide as fusing assistant, its mass ratio is Na
2CO
3: Bi
2O
3: W
AlwaysEqual 20: 20: 100, place the platinum crucible of adding a cover once more 1000 ℃ of thermal treatments 10 hours.At last with product pulverizing, fine grinding, sieve, become piece through isostatic cool pressing.To press caked raw material to pack in the platinum growth crucible, growth crucible is placed in the reactors shown in Figure 1 again.After intensification was melted raw material fully, after 30 ℃ of heat, insulation 20h made the abundant convection current of pyrosol, mixes.Make temperature slowly reduce to solution saturation point temperature, adopting < 001>direction NBBT monocrystalline is seed crystal, and the selection rate of pulling is that 0.5mm/day, rotating speed are that 6rpm carries out the NBBT crystal growth.In the crystal growing process, with the cooling of the rate of temperature fall of 3 ℃/day, and in body of heater aerating oxygen.After crystal breaks away from liquid level, stop to lift, be cooled to room temperature with the rate of temperature fall of 200 ℃/h, obtaining chemical constitution formula is 0.95Na
0.5Bi
0.5TiO
3-0.05BaTiO
3The adulterated bismuth sodium titanate-barium titanate leadless piezoelectric of the manganese of-0.2at%Mn monocrystalline.
Through detecting, can know that by present embodiment the preparation method of the top seed crystal flux pulling technique growth Mn doping NBBT monocrystalline that provides can grow size and reach Φ 35mm * 10mm, piezoelectric constant d
33Reach 500pC/N, electromechanical coupling factor k
tReach 60% the unleaded monocrystalline of high tension performance.
Take by weighing purity and be 99.99% 70.94g yellow soda ash, 311.84g bismuth oxide, 243.56g titanium oxide (excessive 1.6 times), 72.05g barium carbonate (excessive 1.6 times) and 2.45g Manganse Dioxide, dry back-mixing and ball milling was placed in the platinum crucible of adding a cover 1000 ℃ of thermal treatments 10 hours in 20 hours.Then with the products therefrom fine grinding, sieve, based on the total amount W of polycrystal raw material yellow soda ash, bismuth oxide, titanium oxide and barium carbonate
AlwaysAdd a certain proportion of yellow soda ash and bismuth oxide as fusing assistant, its mass ratio is Na
2CO
3: Bi
2O
3: W
AlwaysEqual 15: 15: 100, place the platinum crucible of adding a cover once more 1000 ℃ of thermal treatments 10 hours.At last with product pulverizing, fine grinding, sieve, become piece through isostatic cool pressing.To press caked raw material to pack in the platinum growth crucible, growth crucible is placed in the reactors shown in Figure 1 again.After intensification was melted raw material fully, after 30 ℃ of heat, insulation 20h made the abundant convection current of pyrosol, mixes.Make temperature slowly reduce to solution saturation point temperature, adopting < 001>direction NBBT monocrystalline is seed crystal, and the selection rate of pulling is that 1.0mm/day, rotating speed are that 10rpm carries out the NBBT crystal growth.In the crystal growing process, with the cooling of the rate of temperature fall of 4 ℃/day, and in body of heater aerating oxygen.After crystal breaks away from liquid level, stop to lift, be cooled to room temperature with the rate of temperature fall of 150 ℃/h, obtaining chemical constitution formula is 0.95Na
0.5Bi
0.5TiO
3-0.05BaTiO
3The adulterated bismuth sodium titanate-barium titanate leadless piezoelectric of the manganese of-0.2at%Mn monocrystalline.
Through detecting, can know that by present embodiment the preparation method of the top seed crystal flux pulling technique growth Mn doping NBBT monocrystalline that provides can grow size and reach Φ 35mm * 10mm, piezoelectric constant d
33Reach 500pC/N, electromechanical coupling factor k
tReach 60% the unleaded monocrystalline of high tension performance.
Take by weighing purity and be 99.99% 69.31 yellow soda ash, 304.66 bismuth oxides, 243.22 titanium oxide (excessive 1.2 times), 84.7g barium carbonate (excessive 1.2 times) and 2.44g Manganse Dioxide, dry back-mixing and ball milling was placed in the platinum crucible of adding a cover 1000 ℃ of thermal treatments 10 hours in 20 hours.Then with the products therefrom fine grinding, sieve, based on the total amount W of polycrystal raw material yellow soda ash, bismuth oxide, titanium oxide and barium carbonate
AlwaysAdd a certain proportion of yellow soda ash and bismuth oxide as fusing assistant, its mass ratio is Na
2CO
3: Bi
2O
3: W
AlwaysEqual 20: 20: 100, place the platinum crucible of adding a cover once more 1000 ℃ of thermal treatments 10 hours.At last with product pulverizing, fine grinding, sieve, become piece through isostatic cool pressing.To press caked raw material to pack in the platinum growth crucible, growth crucible is placed in the reactors shown in Figure 1 again.After intensification was melted raw material fully, after 30 ℃ of heat, insulation 20h made the abundant convection current of pyrosol, mixes.Make temperature slowly reduce to solution saturation point temperature, adopting < 001>direction NBBT monocrystalline is seed crystal, and the selection rate of pulling is that 1.5mm/day, rotating speed are that 15rpm carries out the NBBT crystal growth.In the crystal growing process, with the cooling of the rate of temperature fall of 5 ℃/day, and in body of heater aerating oxygen.After crystal breaks away from liquid level, stop to lift, be cooled to room temperature with the rate of temperature fall of 50 ℃/h, obtaining chemical constitution formula is 0.93Na
0.5Bi
0.5TiO
3-0.07BaTiO
3The adulterated bismuth sodium titanate-barium titanate leadless piezoelectric of the manganese of-0.2at%Mn monocrystalline.
Through detecting, can know that by present embodiment the preparation method of the top seed crystal flux pulling technique growth Mn doping NBBT monocrystalline that provides can grow size and reach Φ 35mm * 10mm, piezoelectric constant d
33Reach 500pC/N, electromechanical coupling factor k
tReach 60% the unleaded monocrystalline of high tension performance.
Claims (10)
1. the adulterated bismuth sodium titanate-barium titanate leadless piezoelectric of manganese monocrystalline, its Chemical Composition meets chemical constitution formula (1-x) Na
0.5Bi
0.5TiO
3-xBaTiO
3-y at%Mn, 0＜x＜1,0.1≤y≤0.4 wherein, on behalf of Mn, y at% account for (1-x) Na
0.5Bi
0.5TiO
3-xBaTiO
3Molar percentage.
2. the adulterated bismuth sodium titanate-barium titanate leadless piezoelectric of manganese as claimed in claim 1 monocrystalline is characterized in that 0.05≤x≤0.07, y=0.2.
3. according to claim 1 or claim 2 the preparation method of the adulterated bismuth sodium titanate-barium titanate leadless piezoelectric of manganese monocrystalline comprises the steps:
1), according to chemical constitution formula (1-x) Na
0.5Bi
0.5TiO
3-xBaTiO
3Stoichiometric ratio weighing sodium carbonate and the bismuth oxide of middle Na and Bi; Take by weighing titanium oxide and barium carbonate respectively according to the excessive respectively 1-2 of the stoichiometric ratio of Ti and Ba in said chemical constitution formula amount doubly; Take by weighing Manganse Dioxide again, total mole the molar percentage that said Manganse Dioxide accounts for yellow soda ash, bismuth oxide, titanium oxide and barium carbonate is 1-2at%;
2), the raw material that takes by weighing is added solubility promoter: yellow soda ash and bismuth oxide, ball milling also mixes;
3), the material briquetting that mixes being obtained rising of crystal growth expects;
4), will rise to expect and put into the crucible of monocrystal growing furnace; Be heated to the fusing fully of expecting; Insulation is expected to rising of fusing and to mix, and adopting < O01>direction NBBT monocrystalline is that seed crystal carries out crystal growth, obtains the adulterated bismuth sodium titanate-barium titanate leadless piezoelectric of said manganese monocrystalline after the cooling.
4. the preparation method of the adulterated bismuth sodium titanate-barium titanate leadless piezoelectric of manganese as claimed in claim 3 monocrystalline is characterized in that said step 2) the middle solubility promoter raw material elder generation milling mixing before that adds, put into the crucible sintering again, then fine grinding.
5. the preparation method of the adulterated bismuth sodium titanate-barium titanate leadless piezoelectric of manganese as claimed in claim 3 monocrystalline is characterized in that, the material in the said step 3) before the briquetting is put into the crucible sintering earlier, then pulverizing, fine grinding.
6. the preparation method of the adulterated bismuth sodium titanate-barium titanate leadless piezoelectric of manganese as claimed in claim 3 monocrystalline; It is characterized in that the total mass ratio of yellow soda ash, bismuth oxide, titanium oxide and barium carbonate is (15-20) in the yellow soda ash in the said solubility promoter, bismuth oxide and the raw material: (15-20): 100.
7. the preparation method of the adulterated bismuth sodium titanate-barium titanate leadless piezoelectric of manganese as claimed in claim 3 monocrystalline; It is characterized in that in the step 4), the thermograde of solid-liquid interface is 5～100 ℃/cm in the said monocrystal growing furnace; The seed rod speed of rotation is 6～15rpm; The rate of pulling is 0.5～1.5mm/day, and the rate of temperature fall in the crystal growing process is 3～5 ℃/day, and crystal growth is reduced to room temperature with the rate of temperature fall of 50～200 ℃/h after accomplishing.
8. like the preparation method of claim 3, the adulterated bismuth sodium titanate-barium titanate leadless piezoelectric of 4 or 5 described manganese monocrystalline, it is characterized in that said crucible is selected from platinum crucible.
9. the preparation method of the adulterated bismuth sodium titanate-barium titanate leadless piezoelectric of manganese as claimed in claim 3 monocrystalline is characterized in that in the step 3), said briquetting is selected from the isostatic cool pressing briquetting; In the step 4), said monocrystal growing furnace adopts SiC or MoSi
2The rod heating, atmosphere is oxygen in the body of heater.
10. according to claim 1 or claim 2 the adulterated bismuth sodium titanate-barium titanate leadless piezoelectric of manganese monocrystalline is in high-frequency transducer, industrial flaw detection and medical supersonic engineering Application for Field.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2015055034A1 (en) * | 2013-10-14 | 2015-04-23 | 中国科学院上海硅酸盐研究所 | Lead-free high-voltage active crystal material and preparation method therefor |
| CN106045501A (en) * | 2016-06-01 | 2016-10-26 | 北京中科奥倍超声波技术研究院 | Lead-free piezoelectric ceramic and preparation method thereof |
| CN107008636A (en) * | 2017-05-11 | 2017-08-04 | 上海师范大学 | A kind of leadless piezoelectric monocrystalline high-frequency transducer and preparation method thereof |
| CN116023132A (en) * | 2022-12-30 | 2023-04-28 | 哈尔滨商业大学 | Bismuth sodium titanate-based ceramic with high strain property induced by B-O site defect and preparation method thereof |
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| WO2015055034A1 (en) * | 2013-10-14 | 2015-04-23 | 中国科学院上海硅酸盐研究所 | Lead-free high-voltage active crystal material and preparation method therefor |
| CN106045501A (en) * | 2016-06-01 | 2016-10-26 | 北京中科奥倍超声波技术研究院 | Lead-free piezoelectric ceramic and preparation method thereof |
| CN107008636A (en) * | 2017-05-11 | 2017-08-04 | 上海师范大学 | A kind of leadless piezoelectric monocrystalline high-frequency transducer and preparation method thereof |
| CN116023132A (en) * | 2022-12-30 | 2023-04-28 | 哈尔滨商业大学 | Bismuth sodium titanate-based ceramic with high strain property induced by B-O site defect and preparation method thereof |
| CN116023132B (en) * | 2022-12-30 | 2023-12-01 | 哈尔滨商业大学 | Bismuth sodium titanate-based ceramic with high strain property induced by B-O site defect and preparation method thereof |
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