CN102817068B - A kind of preparation method of sodium bismuth titanate-lead titanate piezoelectric monocrystal - Google Patents
A kind of preparation method of sodium bismuth titanate-lead titanate piezoelectric monocrystal Download PDFInfo
- Publication number
- CN102817068B CN102817068B CN201210324696.4A CN201210324696A CN102817068B CN 102817068 B CN102817068 B CN 102817068B CN 201210324696 A CN201210324696 A CN 201210324696A CN 102817068 B CN102817068 B CN 102817068B
- Authority
- CN
- China
- Prior art keywords
- single crystal
- temperature
- nbt
- lead
- crucible
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- FSAJRXGMUISOIW-UHFFFAOYSA-N bismuth sodium Chemical compound [Na].[Bi] FSAJRXGMUISOIW-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000013078 crystal Substances 0.000 claims abstract description 82
- 238000000034 method Methods 0.000 claims abstract description 25
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 22
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 19
- 239000007858 starting material Substances 0.000 claims description 17
- 238000005303 weighing Methods 0.000 claims description 16
- 238000000498 ball milling Methods 0.000 claims description 15
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 11
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 11
- 229910000464 lead oxide Inorganic materials 0.000 claims description 11
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims description 11
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 11
- 238000003746 solid phase reaction Methods 0.000 claims description 11
- 239000004408 titanium dioxide Substances 0.000 claims description 11
- 238000005245 sintering Methods 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 10
- 238000009694 cold isostatic pressing Methods 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 238000000462 isostatic pressing Methods 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 6
- 239000010410 layer Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 229910003237 Na0.5Bi0.5TiO3 Inorganic materials 0.000 claims description 4
- 229910003781 PbTiO3 Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims description 3
- 239000002356 single layer Substances 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 230000008878 coupling Effects 0.000 abstract description 6
- 238000010168 coupling process Methods 0.000 abstract description 6
- 238000005859 coupling reaction Methods 0.000 abstract description 6
- 230000005684 electric field Effects 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 230000028161 membrane depolarization Effects 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 4
- 230000010287 polarization Effects 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000002457 bidirectional effect Effects 0.000 description 2
- NKZSPGSOXYXWQA-UHFFFAOYSA-N dioxido(oxo)titanium;lead(2+) Chemical compound [Pb+2].[O-][Ti]([O-])=O NKZSPGSOXYXWQA-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 229910002115 bismuth titanate Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 230000005621 ferroelectricity Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920000334 poly[3-(3'-N,N,N-triethylamino-1-propyloxy)-4-methylthiophene-2,5-diyl hydrochloride] polymer Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention discloses a kind of preparation method of sodium bismuth titanate-lead titanate piezoelectric monocrystal, described method is falling crucible method, comprise preparation single crystal growing rise expect, adopts falling crucible method carry out single crystal growing and growth end, be cooled to the steps such as room temperature.The sodium bismuth titanate-lead titanate piezoelectric monocrystal (NBT-PT) that the present invention adopts falling crucible method to obtain to have high-curie temperature and depolarize temperature first, obtained NBT-PT monocrystalline size not only can be made to reach Ф 20mm × 70mm, and make obtained NBT-PT monocrystalline show excellent piezoelectric property and good electric field stability, Curie temperature can reach 300 DEG C, umpolarization temperature can reach 176 DEG C, piezoelectric constant d
33280pC/N can be reached, electromechanical coupling factor k
tcan 52% be reached, there is wide use temperature scope; And lead tolerance is extremely low, meet China and International Environmental Protection demand, therefore its application prospect is very wide.
Description
Technical Field
The invention relates to a preparation method of a relaxor ferroelectric single crystal, in particular to a sodium bismuth titanate-lead titanate piezoelectric single crystal [ (1-x) Na)0.5Bi0.5TiO3-x PbTiO3Abbreviated as NBT-PT]Belonging to the technical field of single crystal growth.
Background
Lead-based complex perovskite-type relaxor ferroelectric single crystal represented by PMNT and PZNT is prepared by virtue of excellent piezoelectric propertiesIs receiving attention as d33And k33Respectively reaching more than 2500pC/N and 92 percent, the maximum strain is more than 1.7 percent, the material has wide application in ultrasonic transducers, piezoelectric transformers, filters, ultrasonic motors and the like, and occupies a great proportion in the field of electronic materials as an important functional material. However, although these materials have very excellent electrical properties, their low curie temperature and trigonal-tetragonal phase transition temperature limit their temperature use range. In addition, in the lead-based material, the content of lead exceeds 60%, which brings serious harm to the environment and ecology. Therefore, it is a hot topic of interest in various countries in the world to research and develop lead-free or lead-less relaxor ferroelectric single crystal materials by increasing the curie temperature and the trigonal-tetragonal phase transition temperature of piezoelectric materials.
Sodium bismuth titanate Na0.5Bi0.5TiO3(NBT for short) is a perovskite ferroelectric having a three-dimensional structure at room temperature and has high ferroelectricity (remanent polarization P)rReach 38 mu C/cm2) Small dielectric constant, good acoustic performance and the like, and is suitable for the fields of high-frequency ultrasonic transducers, industrial flaw detection, medical ultrasonic engineering and the like. But the application of the material is restricted by the higher coercive electric field and the lower depolarization temperature of the material. The occurrence of a bismuth sodium titanate-barium titanate (NBT-BT) solid solution system effectively improves the piezoelectric performance, particularly near the Morphotropic Phase Boundary (MPB), but the leakage current is large and the polarization process is still difficult. Recent studies have shown that a novel sodium bismuth titanate-lead titanate (NBT-PT) system has curie and depolarization temperatures of 340 and 200 ℃ respectively, around the morphotropic phase boundary x =0.11, and up to about 80 ℃ higher than the NBT-BT system. However, no reports on the related art for preparing large-size NBT-PT single crystals by using a Bridgman method have been found so far.
Disclosure of Invention
In view of the above problems in the prior art, the present invention aims to provide a method for preparing a large-size bismuth sodium titanate-lead titanate piezoelectric single crystal by using a Bridgman method.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of sodium bismuth titanate-lead titanate piezoelectric single crystal is a Bridgman method, and comprises the following steps:
a) according to the general formula (1-x) Na0.5Bi0.5TiO3-xPbTiO3Wherein 0 is<x<1, accurately weighing raw materials of sodium carbonate, bismuth oxide, titanium dioxide and lead oxide in stoichiometric ratio to prepare a single crystal growth starting material;
b) loading the prepared single crystal growth starting material into a crucible, adding seed crystals, and performing single crystal growth by adopting a Bridgman method: controlling the temperature of a single crystal growth furnace to be 1380-1500 ℃, keeping the temperature of a melt for 3-10 hours, controlling the temperature rise rate of the furnace in the crystal growth process to be 0-3 ℃/day, the crucible descending rate to be 0.2-1 mm/h, the temperature gradient of a solid-liquid interface to be 5-10 ℃/mm, and the maximum temperature gradient in the crucible descending direction to be 1-7 ℃/mm;
c) and after the growth is finished, cooling to room temperature.
As a preferred embodiment, the operation of preparing the single crystal growth starting material is as follows:
according to the general formula (1-x) Na0.5Bi0.5TiO3-xPbTiO3Wherein 0 is<x<1, accurately weighing sodium carbonate, bismuth oxide, titanium dioxide and lead oxide in stoichiometric ratio, ball-milling to fully and uniformly mix, and then forming blocks by cold isostatic pressing or unequal isostatic pressing to be used as starting materials for single crystal growth.
As another preferred embodiment, the operation of preparing the single crystal growth starting material is as follows:
according to the general formula (1-x) Na0.5Bi0.5TiO3-xPbTiO3Wherein 0 is<x<1, accurately weighing sodium carbonate, bismuth oxide, titanium dioxide and lead oxide in stoichiometric ratio, ball-milling to fully mix, then carrying out solid phase reaction for 4-6 hours at 1000 +/-100 ℃, and sinteringAnd (3) forming a mixture of NBT-PT, finely grinding, and forming blocks by cold isostatic pressing or unequal isostatic pressing to obtain the initial material for single crystal growth.
As another preferred embodiment, the operation of preparing the single crystal growth starting material is as follows:
1) according to the chemical formula Na0.5Bi0.5TiO3Accurately weighing sodium carbonate and bismuth oxide in a stoichiometric ratio, ball-milling to uniformly mix, then carrying out solid phase reaction at 1000 +/-100 ℃ for 4-6 hours, and sintering to obtain a polycrystalline material of NBT;
2) according to the chemical formula PbTiO3Accurately weighing titanium dioxide and lead oxide in stoichiometric ratio (PT for short), ball-milling to uniformly mix, carrying out solid phase reaction at 1000 +/-100 ℃ for 4-6 hours, and sintering to obtain a PT polycrystal material;
3) according to the general formula (1-x) Na0.5Bi0.5TiO3-xPbTiO3Wherein 0 is<x<Accurately weighing NBT and PT polycrystal materials in a stoichiometric ratio, ball-milling to uniformly mix, carrying out solid phase reaction at 1000 +/-100 ℃ for 4-6 hours, sintering to obtain a mixture of NBT-PT, finely grinding, and carrying out cold isostatic pressing to obtain blocks or unequal isostatic pressing to obtain the initial material for single crystal growth.
In a further preferable scheme, the purity of each raw material of the sodium carbonate, the bismuth oxide, the titanium dioxide and the lead oxide is more than 99.99%.
In a further preferred embodiment, the crucible is a platinum crucible.
More preferably, the crucible is a sealed single-layer structure or a sealed double-layer structure or a sealed three-layer structure, and the thickness of each layer is 0.10-0.20 mm.
As a further preferable scheme, the seed crystal is NBT-PT single crystal or lead magnesium niobate-lead titanate (PMN-PT) single crystal with similar lattice structure, and the orientation of the seed crystal is <111>, <110> or <100 >.
As a further preferred scheme, the seed crystal is a NBT-PT single crystal with <110> orientation.
In a further preferable scheme, the size of the seed crystal is phi (19-20) mm multiplied by 50 mm.
As a further preferable scheme, the growth is stopped when the crucible descends by 5cm, and then the temperature is reduced to the room temperature at the temperature reduction rate of 50-200 ℃/h.
As a further preferable embodiment, the general formula (1-x) Na0.5Bi0.5TiO3-xPbTiO30.01. ltoreq. x.ltoreq.0.14, preferably x = 0.09.
Compared with the prior art, the invention adopts the Bridgman method to prepare the sodium bismuth titanate-lead titanate piezoelectric single crystal (NBT-PT) with high Curie temperature and depolarization temperature for the first time, not only can the prepared NBT-PT single crystal reach the size of phi 20mm multiplied by 70mm, but also the prepared NBT-PT single crystal shows excellent piezoelectric performance and good electric field stability, the Curie temperature can reach 300 ℃, the depolarization temperature can reach 176 ℃, and the piezoelectric constant d can reach33Can reach 280pC/N, electromechanical coupling coefficient ktCan reach 52 percent, and has wide application temperature range; and the lead content is extremely low, and the method meets the requirements of China and international environmental protection, so that the method has a very wide application prospect.
Drawings
FIG. 1 is an XRD pattern of a sodium bismuth titanate-lead titanate piezoelectric single crystal obtained in example 1;
FIG. 2 shows the dielectric constants of the sodium bismuth titanate-lead titanate piezoelectric single crystals obtained in example 1 ((r) Graph of dielectric loss (tan) as a function of temperature (deg.C);
FIG. 3 is a hysteresis chart and a bidirectional strain chart of the bismuth sodium titanate-lead titanate piezoelectric single crystal obtained in example 1;
FIG. 4 is a graph showing the thickness vibration mode of the sodium bismuth titanate-lead titanate piezoelectric single crystal obtained in example 1 as a function of impedance (. omega.), phase angle (. degree.) and frequency (Hz).
Detailed Description
The invention is described in more detail and fully below with reference to the accompanying drawings and examples.
Piezoelectric coefficient d according to the invention33Is ZJ-3A type d manufactured by acoustic research of Chinese academy of sciences33The tester directly measures the test result; the dielectric constant is obtained by converting a sample capacitance measured by an HP4192A type impedance analyzer; coefficient of electromechanical coupling ktThe measurement is carried out according to the IEEE176-78 standard by measuring the impedance at different frequencies with an HP4294A type impedance analyzer according to the formulaCalculated, wherein Δ f ═ fp-fs(ii) a The hysteresis loop and the field strain loop were measured by a model Aixacct TF-1000 ferroelectric analysis system.
Example 1
According to the formula 0.91Na0.5Bi0.5TiO3-0.09PbTiO3Accurately weighing the raw materials of sodium carbonate, bismuth oxide, titanium dioxide and lead oxide powder with the stoichiometric ratio of more than 99.99 percent and fully dried, and ball-milling for 24 hours to uniformly mix; then placing the mixture into a covered platinum crucible, and sintering the mixture for 6 hours at 1000 ℃; crushing, fine grinding, sieving and cold isostatic pressing the sintered product to form blocks which are used as starting materials for single crystal growth;
selecting a single-layer platinum crucible with the phi of 20mm multiplied by 200mm as a growth crucible, and taking an NBT-PT single crystal with the size of phi of 19.5mm multiplied by 50mm and the orientation of <110> as a seed crystal; the crucible is sealed after the seed crystal and the starting material for single crystal growth are charged, and then placed in a growth furnace (the present invention is not limited to a growth apparatus, as long as a growth furnace apparatus having a temperature gradient can be used in the present invention, and various patents of Shanghai silicate have been disclosed in this respect, for example, CN 1113970A); adopting a Bridgman method to carry out single crystal growth: controlling the temperature of a single crystal growth furnace to 1390 ℃, keeping the temperature of a melt for 6 hours, controlling the temperature rise rate of the furnace temperature in the crystal growth process to be 2 ℃/day, the crucible descending rate to be 0.3mm/h, the temperature gradient of a solid-liquid interface to be 7 ℃/mm, and the maximum temperature gradient in the crucible descending direction to be 7 ℃/mm;
stopping growing when the crucible descends by 5cm, and then cooling to room temperature at a cooling rate of 50 ℃/hour to obtain a complete NBT-PT single crystal which is consistent with the direction of the seed crystal and has the same shape as the crucible, wherein the seed crystal part of the obtained single crystal is removed, and the size of the ingot part is phi 20mm multiplied by 70 mm.
FIG. 1 is an XRD pattern of the piezoelectric single crystal of sodium bismuth titanate-lead titanate obtained in this example, and it can be seen from FIG. 1 that: the NBT-PT single crystal presents a pure three-dimensional perovskite phase structure at room temperature.
FIG. 2 shows the dielectric constants of the sodium bismuth titanate-lead titanate piezoelectric single crystal produced in this example (r) The dielectric loss (tan) as a function of temperature (c) is shown in fig. 2: the depolarization temperature of the NBT-PT single crystal can reach 176 ℃, and the Curie temperature can reach 300 ℃.
FIG. 3 shows the hysteresis and bidirectional strain charts of the bismuth sodium titanate-lead titanate piezoelectric single crystal produced in this example, and it can be seen from FIG. 3 that: the coercive electric field of the NBT-PT single crystal can reach 43kV/cm, and the residual polarization strength can reach 23 mu C/cm2The maximum strain reaches 0.17%, and the piezoelectric constant can reach 280 pC/N;
FIG. 4 is a graph showing the relationship between the impedance (Ω), phase angle (DEG) and frequency (Hz) of the thickness mode of the piezoelectric single crystal of sodium bismuth titanate-lead titanate obtained in the present example, and it is found from FIG. 4 and calculation according to IEEE standard that the electromechanical coupling coefficient of the thickness mode of the NBT-PT single crystal reaches 52%.
Example 2
This embodiment differs from embodiment 1 only in that:
the operation for preparing the single crystal growth starting material is as follows: according to the general formula 0.99Na0.5Bi0.5TiO3-0.01PbTiO3Accurately weighing the raw materials of sodium carbonate, bismuth oxide, titanium dioxide and lead oxide powder with the stoichiometric ratio of more than 99.99 percent and fully dried, and ball-milling for 24 hours to uniformly mix; then the mixture is cold isostatic pressed into blocks or is unequal isostatic pressed into blocks which are used as the starting material for the growth of the single crystal.
The rest of the description is the same as that in example 1.
The experimental results show that: the crystal ingot can grow according to the embodiment, the crystal ingot size can reach phi 20mm multiplied by 70mm, the Curie temperature is about 300 ℃, the depolarization temperature is about 176 ℃, and the piezoelectric constant d33Reaching 280pC/N, electromechanical coupling coefficient ktMore than 50% of high Curie temperature and less lead titanate piezoelectric single crystal.
Example 3
This embodiment differs from embodiment 1 only in that:
the operation for preparing the single crystal growth starting material is as follows:
1) according to the chemical formula Na0.5Bi0.5TiO3Accurately weighing sodium carbonate and bismuth oxide with the purity of more than 99.99 percent according to the stoichiometric ratio, ball-milling for 24 hours to uniformly mix, then carrying out solid phase reaction for 4 hours at 1100 ℃, and sintering to obtain a polycrystalline material of NBT;
2) according to the chemical formula PbTiO3Accurately weighing titanium dioxide and lead oxide with the stoichiometric ratio and the purity of more than 99.99 percent, ball-milling for 24 hours to uniformly mix, then carrying out solid phase reaction for 4 hours at 1100 ℃, and sintering into PT polycrystal;
3) according to the formula 0.86Na0.5Bi0.5TiO3-0.14PbTiO3Accurately weighing NBT and PT polycrystal materials in stoichiometric ratio, ball-milling for 24 hours to mix uniformly, and then carrying out solid phase reaction for 6 hours at 1100 DEG CSintering into a mixed material of NBT-PT, finely grinding, and forming into blocks by cold isostatic pressing or unequal isostatic pressing to be used as a starting material for single crystal growth.
The rest of the description is the same as that in example 1.
The experimental results show that: the crystal ingot can grow according to the embodiment, the crystal ingot size can reach phi 20mm multiplied by 70mm, the Curie temperature is about 300 ℃, the depolarization temperature is about 176 ℃, and the piezoelectric constant d33Reaching 280pC/N, electromechanical coupling coefficient ktMore than 50% of high Curie temperature and less lead titanate piezoelectric single crystal.
Finally, it must be said here that: the above embodiments are only used for further detailed description of the technical solutions of the present invention, and should not be understood as limiting the scope of the present invention, and the insubstantial modifications and adaptations made by those skilled in the art according to the above descriptions of the present invention are within the scope of the present invention.
Claims (6)
1. A preparation method of sodium bismuth titanate-lead titanate piezoelectric single crystal is characterized in that the method is a Bridgman method, and comprises the following specific steps:
a) the preparation method of the single crystal growth starting material comprises the following specific operations:
according to the general formula (1-x) Na0.5Bi0.5TiO3-xPbTiO3Accurately weighing sodium carbonate, bismuth oxide, titanium dioxide and lead oxide in stoichiometric ratio, ball-milling to fully mix, and then forming blocks by cold isostatic pressing or unequal isostatic pressing to be used as starting materials for single crystal growth;
or,
according to the general formula (1-x) Na0.5Bi0.5TiO3-xPbTiO3Accurately weighing sodium carbonate, bismuth oxide, titanium dioxide and lead oxide in stoichiometric ratio, ball-milling to fully mix, then carrying out solid phase reaction at 1000 +/-100 ℃ for 4-6 hours, sintering to obtain a mixture of NBT-PT, finely grinding, and forming blocks by cold isostatic pressing or unequal isostatic pressing to obtain a starting material for single crystal growth;
or,
a1) according to the chemical formula Na0.5Bi0.5TiO3Accurately weighing sodium carbonate and bismuth oxide in a stoichiometric ratio, ball-milling to uniformly mix, then carrying out solid phase reaction at 1000 +/-100 ℃ for 4-6 hours, and sintering to obtain a polycrystalline material of NBT;
a2) according to the chemical formula PbTiO3Accurately weighing titanium dioxide and lead oxide in a stoichiometric ratio, ball-milling to uniformly mix, carrying out solid phase reaction at 1000 +/-100 ℃ for 4-6 hours, and sintering to obtain a PT polycrystal material;
a3) according to the general formula (1-x) Na0.5Bi0.5TiO3-xPbTiO3Accurately weighing NBT and PT polycrystal materials in a stoichiometric ratio, ball-milling to uniformly mix, then carrying out solid phase reaction at 1000 +/-100 ℃ for 4-6 hours, sintering to obtain a mixture of NBT-PT, finely grinding, and carrying out cold isostatic pressing to obtain blocks or unequal isostatic pressing to obtain blocks serving as a single crystal growth starting material;
b) loading the prepared single crystal growth starting material into a crucible, adding seed crystals, and performing single crystal growth by adopting a Bridgman method: controlling the temperature of a single crystal growth furnace to be 1380-1500 ℃, keeping the temperature of a melt for 3-10 hours, controlling the temperature rise rate of the furnace in the crystal growth process to be 0-3 ℃/day, the crucible descending rate to be 0.2-1 mm/h, the temperature gradient of a solid-liquid interface to be 5-10 ℃/mm, and the maximum temperature gradient in the crucible descending direction to be 1-7 ℃/mm;
c) after the growth is finished, cooling to room temperature;
the general formula (1-x) Na0.5Bi0.5TiO3-xPbTiO3Wherein x is more than or equal to 0.01 and less than or equal to 0.14.
2. The method of claim 1, wherein: the crucible is a platinum crucible.
3. The method of claim 2, wherein: the crucible adopts a sealed single-layer or double-layer or three-layer structure, and the thickness of each layer is 0.10-0.20 mm.
4. The method of claim 1, wherein: the seed crystal is NBT-PT single crystal or lead magnesium niobate-lead titanate single crystal with similar lattice structure, and the orientation of the seed crystal is <111>, <110> or <100 >.
5. The method of claim 1, wherein: the size of the seed crystal is phi (19-20) mm multiplied by 50 mm.
6. The method of claim 1, wherein: stopping growth when the crucible descends by 5cm, and then reducing the temperature to room temperature at a cooling rate of 50-200 ℃/h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210324696.4A CN102817068B (en) | 2012-09-04 | 2012-09-04 | A kind of preparation method of sodium bismuth titanate-lead titanate piezoelectric monocrystal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210324696.4A CN102817068B (en) | 2012-09-04 | 2012-09-04 | A kind of preparation method of sodium bismuth titanate-lead titanate piezoelectric monocrystal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102817068A CN102817068A (en) | 2012-12-12 |
| CN102817068B true CN102817068B (en) | 2015-10-28 |
Family
ID=47301497
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210324696.4A Expired - Fee Related CN102817068B (en) | 2012-09-04 | 2012-09-04 | A kind of preparation method of sodium bismuth titanate-lead titanate piezoelectric monocrystal |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102817068B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105624791B (en) * | 2014-10-28 | 2018-05-08 | 中国科学院上海硅酸盐研究所 | A kind of preparation method of Tetragonal titanium magnesium acid bismuth-lead titanate piezoelectric monocrystal |
| CN113113582B (en) * | 2021-03-19 | 2022-11-22 | 上海利物盛纳米科技有限公司 | Preparation method of graphene-titanate lead-acid battery electrode active substance additive with layered structure |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020036282A1 (en) * | 1998-10-19 | 2002-03-28 | Yet-Ming Chiang | Electromechanical actuators |
-
2012
- 2012-09-04 CN CN201210324696.4A patent/CN102817068B/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| Growth and some electrical properties of lead-free piezoelectric crystals (Na1/2Bi1/2)TiO3 and (Na1/2Bi1/2)TiO3-BaTiO3 prepared by a Bridgman method;Guisheng Xu, et al.;《Journal of Crystal Growth》;20050101;第275卷;第114-115页 * |
| Structural phase transition study of the morphotropic phase boundary compositions of Na0.5Bi0.5TiO3–PbTiO3;Sarab Preet Singh et al.;《Journal of physics: condensed matter》;20090817;第21卷;第375902(2)页第2和第375902(6)页第3.3部分 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102817068A (en) | 2012-12-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101913868B (en) | Method for preparing potassium-sodium niobate textured ceramic and potassium-sodium niobate single crystal | |
| CN101985775A (en) | Ternary system relaxation ferroelectric single crystal material and preparation method thereof | |
| Moon et al. | Solid state growth of Na1/2Bi1/2TiO3–BaTiO3 single crystals and their enhanced piezoelectric properties | |
| Zhang et al. | Growth and electric properties of 0.96 Na0. 5Bi0. 5TiO3–0.04 BaTiO3 single crystal | |
| CN102817080A (en) | Lead lutetioniobate-lead magnesioniobate-lead titanate ternary-system relaxation ferroelectric monocrystal and preparation method thereof | |
| CN102628186B (en) | Preparation method of quadrature-phase lithium tantalum doped potassium sodium niobate based lead-free piezoelectric single crystal | |
| CN102180665A (en) | Bismuth scandate-lead titanate high-temperature piezoelectric ceramic material and preparation method thereof | |
| JP2011510898A (en) | Method for producing ternary piezoelectric crystal | |
| CN104876567A (en) | High-piezoelectric coefficient potassium-sodium niobate based leadless piezoelectric ceramics and preparation method thereof | |
| CN104419984B (en) | Preparation method of perovskite-structure relaxor ferroelectric single crystal lead indium niobate-lead magnesium niobate-lead titanate | |
| CN103966659B (en) | The preparation method of potassium-sodium niobate KNN monocrystalline | |
| CN103774228A (en) | Lead scandium niobate-lead magnesium diniobate-lead titanate ferroelectric monocrystal and preparation method thereof | |
| Xiong et al. | Growth and high temperature properties of Ca3Ta (Al0. 9Ga0. 1) 3Si2O14 crystals with ordered langasite structure | |
| CN115093216A (en) | Barium titanate doped lead-free ceramic with high electrostriction and low hysteresis and preparation method thereof | |
| CN102817068B (en) | A kind of preparation method of sodium bismuth titanate-lead titanate piezoelectric monocrystal | |
| Guo et al. | Growth and electrical properties of Pb (Sc1/2Nb1/2) O3–Pb (Mg1/3Nb2/3) O3–PbTiO3 ternary single crystals by a modified Bridgman technique | |
| Wang et al. | Growth and characterization of lead-free ferroelectric (K, Na, Li)(Nb, Ta, Sb) O3 single crystal | |
| CN104372409B (en) | Ternary system relaxation base ferroelectric piezoelectric single crystal and its growing method | |
| Wang et al. | Investigation on the phase transition behavior and electrical properties of textured Lix (K0. 48Na0. 52) 1− xNbO3 piezoelectric ceramics | |
| CN103436963A (en) | Preparation method of tantalump-doped potassium-sodium niobate lead-free piezoelectric single crystal with high electromechanical coupling property | |
| CN106521627B (en) | A kind of potassium-sodium niobate-based piezoelectric monocrystal and preparation method thereof | |
| CN102443852A (en) | Manganese-doped sodium bismuth titanate-barium titanate lead-free piezoelectric single crystal and preparation method thereof | |
| CN103435344B (en) | Piezoceramic material for high-frequency ceramic filter | |
| CN102492991A (en) | Lead niobate zincate-lead titanate (PZNT) single crystal material and pyroelectric application thereof | |
| Yuan et al. | Effects of the doping of W6+ ions on the structure and electrical properties of Pb0. 95Ba0. 05Nb2O6 piezoelectric ceramics |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20151028 Termination date: 20160904 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |