CN103774228A - Lead scandium niobate-lead magnesium diniobate-lead titanate ferroelectric monocrystal and preparation method thereof - Google Patents
Lead scandium niobate-lead magnesium diniobate-lead titanate ferroelectric monocrystal and preparation method thereof Download PDFInfo
- Publication number
- CN103774228A CN103774228A CN201410065657.6A CN201410065657A CN103774228A CN 103774228 A CN103774228 A CN 103774228A CN 201410065657 A CN201410065657 A CN 201410065657A CN 103774228 A CN103774228 A CN 103774228A
- Authority
- CN
- China
- Prior art keywords
- crystal
- lead
- pmn
- presoma
- temperature
- 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.)
- Granted
Links
Images
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention relates to a lead scandium niobate-lead magnesium diniobate-lead titanate ferroelectric monocrystal material and a preparation method thereof. The monocrystal material is a perovskite type structure; a chemical general formula of the monocrystal material is expressed as xPb(Scl/2Nb1/2)O3-yPb(Mg1/3Nb2/3)O3-(1-x-y)PbTiO3, wherein x is greater than or equal to 0.01 and less than or equal to 0.10; y is greater than or equal to 0.50 and less than or equal to 0.70; 1-x-y is not equal to 0. The monocrystal is grown by using a bridgman-stockbarger method or a high-temperature solution method. By utilizing the monocrystal material, the defects of low rhombohedral-tetragonal phase change temperature of PMN-PT (lead magnesium diniobate) monocrystals and difficult crystallization and batch growth of PSN-PT (lead titanate) monocrystals in the prior art can be solved; the monocrystal is high in piezoelectric constant and high in rhombohedral-tetragonal phase change temperature, so that the monocrystal can be widely applied to ultrasonic transducers, underwater acoustic transducers and sensors.
Description
Technical field
The present invention relates to a kind of lead scandate columbate-PMN-PT ferro-electricity single crystal and preparation method thereof.Particularly, the present invention relates to and there is higher tripartite-Tetragonal temperature T
rtwith piezoelectric constant d
33ferroelectric single crystal material xPb (Sc
1/2nb
1/2) O
3-yPb (Mg
1/3nb
2/3) O
3-(1-x-y) PbTiO
3, note the PT into xPSN-yPMN-(1-x-y) by abridging, and the preparation method of crystal, structure and electric property, belong to crystal technology and functional materials and learn field.
Background technology
Large size lead zinc niobate-lead titanate [Pb (Zn
1/3nb
2/3) O
3-PbTiO
3, note by abridging as PZN-PT] and PMN-PT [Pb (Mg
1/3nb
2/3) O
3-PbTiO
3brief note is for PMN-PT] birth of relaxation Ferroelectric monocrystalline, with its high tension electricity coefficient, high-k, high strain, a series of extremely excellent performances such as high energy storage density cause the scientist in electronic functional material field and the broad interest of major company and greatly repercussion immediately.These performance index exceed tens times, even hundreds of times than barium titanate (BT) and Pb-based lanthanumdoped zirconate titanates (PZT) piezoelectric ceramics of widespread use already now.Therefore, be considered to ferroelectric material once breathtaking important breakthrough since piezoelectric ceramics came out for five more than ten years.
But, compared with conventional P ZT piezoelectric ceramics, the tripartite of PMN-PT and PZN-PT monocrystalline-cubic ferroelectric phase transition temperature T
rTlower, generally below 100 ℃.Therefore, compared with under elevated operating temperature, PMN-PT and PZN-PT monocrystalline can not replace conventional P ZT piezoelectric ceramics, thereby have greatly limited its range of application.Such as the field such as wide temperature range sensor and performer, electrical condenser used in high power density sonac and driving mechanism, emission type underwater acoustic transducer, automotive industry and space equipment, require piezoelectric to there is higher tripartite-cubic iron transformation temperature T
rT, enough wide to guarantee its working temperature interval, PMN-PT and PZN-PT monocrystalline obviously can not meet service requirements.For this reason, investigators have carried out exploring more widely and studying to the crystal growth of other system Pb-Based Relaxor Ferroelectric Materials, the T of report at present
rTthe material system that higher and other electric property is suitable with PZN-PT monocrystalline with PMN-PT mainly contains lead scandate columbate-lead titanate [Pb (Sc
1/2nb
1/2) O
3-PbTiO
3, note by abridging as PSN-PT], niobium ytterbium lead plumbate-lead titanate [Pb (Yb
1/2nb
1/2) O
3-PbTiO
3, note by abridging as PYN-PT], lead niobate lead indate-lead-lead titanate [Pb (In
1/2nb
1/2) O
3-PbTiO
3, note by abridging as PIN-PT], but this class relaxor ferroelectric monocrystal growth difficulty is difficult to obtain high-quality bulky single crystal.
Research shows, the growth of PSN-PT relaxor ferroelectric crystal mainly faces two hang-ups at present: the one, and the higher (T of this material melting point
m>1425 ℃, the fusing point of PMN-PT and PZN-PT is all no more than 1300 ℃), crystal growing apparatus and crucible are had to higher requirement, and crystallization difficulty, be difficult for growing large-sized monocrystalline; The 2nd, starting material Sc
2o
3expensive, be unfavorable for material cost advantage.
Summary of the invention
The object of the invention is to find a kind of novel ferro-electricity single crystal and study its preparation method based on above-mentioned background, to solve the difficult ferro-electricity single crystal of growing and not being applicable to preferably high power device of existing high tripartite-Tetragonal temperature ferro-electricity single crystal, for ferroelectric single crystal material increases a kind of new variety.This crystalline material can be widely used in piezoelectric device field.
A kind of novel ferroelectric single crystal material provided by the invention: lead scandate columbate-PMN-PT ferro-electricity single crystal, its special feature is: this materials chemistry formula is xPb (Sc
1/2nb
1/2) O
3-yPb (Mg
1/3nb
2/3) O
3-(1-x-y) PbTiO
3, wherein: 0.01≤x≤0.10,0.50≤y≤0.70,1-x-y ≠ 0, belongs to complex perovskite structure.
The chemical constitution of described lead scandate columbate-PMN-PT ferro-electricity single crystal is elected as: x=0.02～0.08, y=0.58～0.68,1-x-y=0.32～0.34.
Preferred ingredient is 0.06 Pb (Sc
1/2nb
1/2) O
3-0.61 Pb (Mg
1/3nb
2/3) O
3-0.33 PbTiO
3.
The method of preparing above-mentioned lead scandate columbate-PMN-PT ferro-electricity single crystal, comprises following concrete steps:
A) with the Nb of 99.9% above purity
2o
5and Sc
2o
3for initial feed is synthesized presoma ScNbO by solid reaction process
4; With the Nb of 99.9% above purity
2o
5and MgO, or Nb
2o
5and 4MgCO
3mg (OH)
24H
2o is that initial feed is synthesized presoma MgNb by solid reaction process
2o
6;
B) according to chemical formula xPb (Sc
1/2nb
1/2) O
3-yPb (Mg
1/3nb
2/3) O
3-(1-x-y) PbTiO
3composition take presoma ScNbO
4, presoma MgNb
2o
6, 99.99% above purity initial feed PbO(or Pb
3o
4) and the initial feed TiO of 99.99% above purity
2, carry out ball milling it mixed, wherein: 0.01≤x≤0.10,0.50≤y≤0.70,1-x-y ≠ 0;
C) raw material mixing is packed in platinum crucible, platinum crucible is added a cover and is placed in crystal growing furnace, adopt falling crucible method to carry out crystal growth, processing parameter comprises: 1350～1470 ℃ of melt district furnace temperature, melt soaking time 12～24 hours, 20～47 ℃/cm of burner hearth axial-temperature gradient, dropping speed of the crucible 0.1～1.5mm/h;
D) after growth finishes, treat that crystal furnace naturally cools to room temperature, peel off crucible and obtain monocrystalline.
Described ball milling is dry ball milling or wet ball grinding, Ball-milling Time 8～20 hours.
The platiniferous purity of described platinum crucible is not less than 99.9%.
The bottom of described platinum crucible is provided with a cylindric crystal selector, and the length-to-diameter ratio of cylindric crystal selector is not less than 1.
The method of the lead scandate columbate-PMN-PT ferro-electricity single crystal described in preparation, comprises following concrete steps:
A) with the Nb of 99.9% above purity
2o
5and Sc
2o
3for initial feed is synthesized presoma ScNbO by solid reaction process
4; With the Nb of 99.9% above purity
2o
5and MgO, or Nb
2o
5and 4MgCO
3mg (OH)
24H
2o is that initial feed is synthesized presoma MgNb by solid reaction process
2o
6;
B) according to chemical formula xPb (Sc
1/2nb
1/2) O
3-yPb (Mg
1/3nb
2/3) O
3-(1-x-y) PbTiO
3composition take presoma ScNbO
4, presoma MgNb
2o
6, 99.99% above purity initial feed PbO(or Pb
3o
4) and the initial feed TiO of 99.99% above purity
2, preparation crystal raw material, wherein: 0.01≤x≤0.10,0.50≤y≤0.70,1-x-y ≠ 0;
C) solubility promoter adopts PbO or the Pb of 99.99% above purity
3o
4, solubility promoter add-on is 50～80% of raw material total mass;
D) crystal raw material and solubility promoter mix through dry method or wet ball grinding, Ball-milling Time 8～20 hours;
E) raw material mixing is packed in platinum crucible, platinum crucible is added a cover and is placed on material in crystal growing furnace, 1200～1350 ℃ of material temperature, soaking time 12～24 hours;
F) after raw material fusing, carry out continuous Slow cooling, processing parameter comprises: it is material temperature that Slow cooling starts temperature, 1～15 ℃/day of Slow cooling speed, 900 ℃ of Slow cooling end temps;
G) Slow cooling cools to room temperature with the furnace after finishing, and falls solubility promoter with hot nitric acid dissolve, can obtain required monocrystalline.
Compared with prior art, the invention has the advantages that:
In PMN-PT system, introduce lead scandate columbate (PSN), changed into ternary system PSN-PMN-PT, compared with PMN-PT, under the prerequisite that does not reduce piezoelectric property, can effectively improve T on the one hand
rT; Compared with PSN-PT, can greatly reduce Sc on the other hand
2o
3consumption, reduce costs, simultaneously can reduce material melting point, make crystal growth become easy.
The falling crucible method adopting can growing large-size crystal, two the important parameter-thermogrades and the dropping speed of the crucible that affect crystal growth quality are easily accurately controlled; Be provided with a cylindric crystal selector in platinum crucible bottom in addition, effectively eliminate the crystal grain of early origin, assurance only has a grain growth to become final crystal, guarantee on the one hand the success ratio of single crystal growing, save on the other hand seed crystal, remove these process procedures of seed crystal preparation, processing and installation, enhanced productivity.
Adopt o technique simple, easy to operate, without seed crystal, equipment investment is little, easily promotes, and has great advantage for small size crystal growth tool.
Can estimate, PSN-PMN-PT ferro-electricity single crystal field such as wide temperature range sensor and performer, electrical condenser used in high power density sonac and driving mechanism, automotive industry and space equipment, overcomes PMN-PT and PZN-PT ferro-electricity single crystal tripartite-Tetragonal temperature T
rTlow shortcoming and being more widely used.This material also can be applicable to the emission type underwater acoustic transducer of sonar system, can improve sensitivity and the energy transformation density of underwater acoustic transducer, increases range of detector and the resolving power of sonar; Be applied to various piezoelectric transducers, driving mechanism and damping noise reduction system in intelligent structure, create immeasurable economic and social benefit.
According to the difference of the ratio of PSN, PMN and PT, tripartite-Tetragonal temperature T of xPSN-yPMN-(1-x-y) the PT monocrystalline growing
rtbetween 107～150 ℃, piezoelectric constant d
33between 700-2600pC/N.
The powder x-ray diffraction result of prepared 0.06PSN-0.61PMN-0.33PT ferroelectric single crystal material shows that its crystalline structure belongs to perovskite structure; (001) bright its tripartite-Tetragonal temperature of the dielectric temperature stave of the crystal cut of direction T
rtbe 142 ℃, approach its Curie temperature T
c(148 ℃), in the time that frequency is 1kHz, the specific inductivity under room temperature reaches 2412, and dielectric loss is 0.01; (001) ferroelectric hysteresis loop of direction crystal cut shows, its coercive field E
cfor 4.043kV/cm, residual polarization P
rbe 44.54 μ C/cm
2; (001) the piezoelectric constant d of direction crystal cut
33reach 2571pC/N.
Accompanying drawing explanation
Fig. 1 is Bridgman-Stockbarge method for growing xPSN-yPMN-(1-x-y) PT monocrystalline platinum crucible shape used;
Fig. 2 is the 0.06PSN-0.61PMN-0.33PT monocrystalline with Bridgman-Stockbarge method for growing;
Fig. 3 is the x-ray diffractogram of powder spectrum under grown 0.06PSN-0.61PMN-0.33PT monocrystalline normal temperature;
The temperature variant dielectric temperature spectrum of DIELECTRIC CONSTANT ε that Fig. 4 is grown 0.06PSN-0.61PMN-0.33PT monocrystalline;
The polarizability P-electric field E ferroelectric hysteresis loop that Fig. 5 is grown 0.06PSN-0.61PMN-0.33PT monocrystalline.
Embodiment
Below in conjunction with specific embodiment, the present invention is done to further detailed, complete explanation, but do not limit content of the present invention.
Crystal growing furnace of the present invention is designed, designed processing, powder x-ray diffraction for structural analysis is Japanese Shimadzu XRD-6000 type, dielectric temperature spectrum adopts the accurate LCR table of the E4980A of Agilent company of the U.S. to connect the alternating temperature testing of equipment of automatic control, the Radiant Precision Workstation Hysteresis Measuring System that ferroelectric hysteresis loop is produced by Radiant company of the U.S. records, piezoelectric constant d
33the ZJ-6A quasistatic piezoelectric constant tester of being produced by Acoustical Inst., Chinese Academy of Sciences records.
A kind of novel ferroelectric single crystal material provided by the invention: lead scandate columbate-PMN-PT ferro-electricity single crystal, this materials chemistry formula is xPb (Sc
1/2nb
1/2) O
3-yPb (Mg
1/3nb
2/3) O
3-(1-x-y) PbTiO
3, note the PT into xPSN-yPMN-(1-x-y) by abridging.
Embodiment 1:
Adopt o growth 0.01PSN-0.66PMN-0.33PT ferro-electricity single crystal.
Press chemical formula ScNbO
4composition take initial feed Nb
2o
5and Sc
2o
3, wet ball grinding mixes it, calcines 3 hours, to synthesize presoma ScNbO after compacting at 1200 ℃
4; Press chemical formula MgNb
2o
6composition take initial feed Nb
2o
5and 4MgCO
3mg (OH)
24H
2o, wet ball grinding mixes it, calcines 6 hours, to synthesize presoma MgNb after compacting at 1000 ℃
2o
6; Take initial feed PbO, TiO according to 0.01PSN-0.66PMN-0.33PT composition
2with presoma ScNbO
4, MgNb
2o
6preparation crystal raw material; Solubility promoter adopts PbO, and solubility promoter add-on is 80% of raw material total mass; Crystal raw material and solubility promoter mix through wet ball grinding, Ball-milling Time 14 hours; The raw material mixing is packed in platinum crucible, and platinum crucible is added a cover and is placed on material in crystal growing furnace, 1300 ℃ of material temperature, soaking time 18 hours; After raw material fusing, carry out continuous Slow cooling, 3 ℃/day of Slow cooling speed, 900 ℃ of Slow cooling end temps; After Slow cooling finishes, cool to room temperature with the furnace, fall solubility promoter with hot nitric acid dissolve, can obtain monocrystalline, monocrystalline overall dimension 3mm × 3mm × 4mm.Appoint and get some single crystal particles and grind and be finely ground to powder for powder x-ray diffraction analysis, result shows that 0.01PSN-0.66PMN-0.33PT crystal is perovskite structure.Obtained monocrystalline is cut to small pieces by (001) direction, section two sides is polished smooth with sand paper, the two sides then polishing smooth at it by silver electrode; Under the DC electric field of 10kV/cm to sample polarization 15 minutes; Place and after 24 hours, the sample polarizing is carried out to piezoelectric property test, measured piezoelectric constant d
33for 887pC/N; After having surveyed piezoelectric constant, carry out the test of dielectric temperature spectrum, result shows the Curie temperature T of sample
cbe that 149 ℃, tripartite-Tetragonal temperature are T
rtit is 90 ℃.
Embodiment 2:
Adopt o growth 0.04PSN-0.63PMN-0.33PT ferro-electricity single crystal.
Presoma ScNbO
4, MgNb
2o
6preparation with embodiment 1, take initial feed PbO, TiO according to 0.04PSN-0.63PMN-0.33PT composition
2with presoma ScNbO
4, MgNb
2o
6preparation crystal raw material; Solubility promoter adopts PbO, and solubility promoter add-on is 80% of raw material total mass; Crystal raw material and solubility promoter mix through wet ball grinding, Ball-milling Time 10 hours; The raw material mixing is packed in platinum crucible, and platinum crucible is added a cover and is placed on material in crystal growing furnace, 1300 ℃ of material temperature, soaking time 10 hours; After raw material fusing, carry out continuous Slow cooling, 8 ℃/day of Slow cooling speed, 900 ℃ of Slow cooling end temps; After Slow cooling finishes, cool to room temperature with the furnace, fall solubility promoter with hot nitric acid dissolve, can obtain monocrystalline, monocrystalline overall dimension 4mm × 4mm × 4mm.Appoint and get some single crystal particles and grind and be finely ground to powder for powder x-ray diffraction analysis, result shows that 0.04PSN-0.63PMN-0.33PT crystal is perovskite structure.Obtained monocrystalline is cut to small pieces by (001) direction, section two sides is polished smooth with sand paper, the two sides then polishing smooth at it by silver electrode; Under the DC electric field of 10kV/cm to sample polarization 15 minutes; Place and after 24 hours, the sample polarizing is carried out to piezoelectric property test, measured piezoelectric constant d
33for 1454pC/N; After having surveyed piezoelectric constant, carry out the test of dielectric temperature spectrum, result shows the Curie temperature T of sample
cbe that 155 ℃, tripartite-Tetragonal temperature are T
rtit is 117 ℃.
Embodiment 3:
Adopt o growth 0.06PSN-0.60PMN-0.34PT ferro-electricity single crystal.
Press chemical formula ScNbO
4composition take initial feed Nb
2o
5and Sc
2o
3, dry ball milling mixes it, calcines 3 hours, to synthesize presoma ScNbO after compacting at 1200 ℃
4; Press chemical formula MgNb
2o
6composition take initial feed Nb
2o
5and MgO, dry ball milling mixes it, calcines 6 hours, to synthesize presoma MgNb after compacting at 1000 ℃
2o
6; Take initial feed Pb according to 0.06PSN-0.60PMN-0.34PT composition
3o
4, TiO
2with presoma ScNbO
4, MgNb
2o
6preparation crystal raw material; Solubility promoter adopts Pb
3o
4, solubility promoter add-on is 55% of raw material total mass; Crystal raw material and solubility promoter mix through dry ball milling, Ball-milling Time 20 hours; The raw material mixing is packed in platinum crucible, and platinum crucible is added a cover and is placed on material in crystal growing furnace, 1275 ℃ of material temperature, soaking time 22 hours; After raw material fusing, carry out continuous Slow cooling, 2 ℃/day of Slow cooling speed, 900 ℃ of Slow cooling end temps; After Slow cooling finishes, cool to room temperature with the furnace, fall solubility promoter with hot nitric acid dissolve, can obtain monocrystalline, monocrystalline overall dimension 6mm × 6mm × 4mm.Appoint and get some single crystal particles and grind and be finely ground to powder for powder x-ray diffraction analysis, result shows that 0.06PSN-0.60PMN-0.34PT crystal is perovskite structure.Obtained monocrystalline is cut to small pieces by (001) direction, section two sides is polished smooth with sand paper, the two sides then polishing smooth at it by silver electrode; Under the DC electric field of 10kV/cm to sample polarization 15 minutes; Place and after 24 hours, the sample polarizing is carried out to piezoelectric property test, measured piezoelectric constant d
33for 2270pC/N; After having surveyed piezoelectric constant, carry out the test of dielectric temperature spectrum, result shows the Curie temperature T of sample
cbe that 154 ℃, tripartite-Tetragonal temperature are T
rtit is 136 ℃.
Embodiment 4:
Adopt o growth 0.08PSN-0.59PMN-0.33PT ferro-electricity single crystal.
Presoma ScNbO
4, MgNb
2o
6preparation with embodiment 3, take initial feed PbO, TiO according to 0.08PSN-0.59PMN-0.33PT composition
2with presoma ScNbO
4, MgNb
2o
6preparation crystal raw material; Solubility promoter adopts PbO, and solubility promoter add-on is 75% of raw material total mass; Crystal raw material and solubility promoter mix through dry ball milling, Ball-milling Time 10 hours; The raw material mixing is packed in platinum crucible, and platinum crucible is added a cover and is placed on material in crystal growing furnace, 1350 ℃ of material temperature, soaking time 12 hours; After raw material fusing, carry out continuous Slow cooling, 9 ℃/day of Slow cooling speed, 900 ℃ of Slow cooling end temps; After Slow cooling finishes, cool to room temperature with the furnace, fall solubility promoter with hot nitric acid dissolve, can obtain monocrystalline, monocrystalline overall dimension 4mm × 4mm × 3mm.Appoint and get some single crystal particles and grind and be finely ground to powder for powder x-ray diffraction analysis, result shows that 0.08PSN-0.59PMN-0.33PT crystal is perovskite structure.Obtained monocrystalline is cut to small pieces by (001) direction, section two sides is polished smooth with sand paper, the two sides then polishing smooth at it by silver electrode; Under the DC electric field of 10kV/cm to sample polarization 15 minutes; Place and after 24 hours, the sample polarizing is carried out to piezoelectric property test, measured piezoelectric constant d
33for 1218pC/N; After having surveyed piezoelectric constant, carry out the test of dielectric temperature spectrum, result shows the Curie temperature T of sample
cbe that 149 ℃, tripartite-Tetragonal temperature are T
rtit is 120 ℃.
Embodiment 5:
Adopt Bridgman-Stockbarge method for growing 0.16PSN-0.49PMN-0.35PT ferroelectric single crystal material.
Press chemical formula ScNbO
4composition take initial feed Nb
2o
5and Sc
2o
3, dry ball milling mixes it, calcines 3 hours, to synthesize presoma ScNbO after compacting at 1200 ℃
4; Press chemical formula MgNb
2o
6composition take initial feed Nb
2o
5and MgO, dry ball milling mixes it, calcines 6 hours, to synthesize presoma MgNb after compacting at 1000 ℃
2o
6; Take initial feed PbO, TiO according to the composition of 0.16PSN-0.49PMN-0.35PT
2with presoma ScNbO
4, MgNb
2o
6, wet ball grinding mixes it; The raw material mixing is packed in platinum crucible, platinum crucible internal diameter 25mm used, bottom is conical; Platinum crucible is added a cover and is placed in crystal growing furnace, adopts falling crucible method to carry out crystal growth, 1435 ℃ of melt district furnace temperature, melt soaking time 18 hours, 27 ℃/cm of burner hearth axial-temperature gradient, dropping speed of the crucible 0.4mm/h; After growth finishes, treat that crystal furnace naturally cools to room temperature, peel off crucible and find that gained crystal is polycrystalline; Obtained polycrystalline is cut to some grindings and be finely ground to powder for powder x-ray diffraction analysis, result shows that 0.16PSN-0.49PMN-0.35PT polycrystalline is perovskite structure.
Embodiment 6:
Adopt Bridgman-Stockbarge method for growing 0.06PSN-0.61PMN-0.33PT ferroelectric single crystal material.
Press chemical formula ScNbO
4composition take initial feed Nb
2o
5and Sc
2o
3, wet ball grinding mixes it, calcines 3 hours, to synthesize presoma ScNbO after compacting at 1200 ℃
4; Press chemical formula MgNb
2o
6composition take initial feed Nb
2o
5and 4MgCO
3mg (OH)
24H
2o, wet ball grinding mixes it, calcines 6 hours, to synthesize presoma MgNb after compacting at 1000 ℃
2o
6; Take initial feed PbO, TiO according to the composition of 0.06PSN-0.61PMN-0.33PT
2with presoma ScNbO
4, MgNb
2o
6, dry ball milling mixes it; The raw material mixing is packed in platinum crucible into platinum crucible used bottom crystal selector internal diameter 5mm, length-to-diameter ratio (length/diameter)=2, platinum crucible main part internal diameter 25mm; Platinum crucible is added a cover and is placed in crystal growing furnace, adopts falling crucible method to carry out crystal growth, 1365 ℃ of melt district furnace temperature, melt soaking time 13 hours, 22 ℃/cm of burner hearth axial-temperature gradient, dropping speed of the crucible 0.5mm/h; After growth finishes, treat that crystal furnace naturally cools to room temperature, peel off crucible and obtain the monocrystalline shown in Fig. 2, its size reaches 25mm × 50mm.
Obtained monocrystalline is cut to a small pieces grinding and be finely ground to powder for powder x-ray diffraction analysis, result shows that 0.06PSN-0.61PMN-0.33PT crystal is perovskite structure.
Obtained monocrystalline is cut to small pieces by (001) direction, section two sides is polished smooth with sand paper, the two sides then polishing smooth at it by silver electrode; Under the DC electric field of 10kV/cm to sample polarization 15 minutes; Place and after 24 hours, the sample polarizing is carried out to piezoelectric property test, measured piezoelectric constant d
33for 2363pC/N; After having surveyed piezoelectric constant, carry out the test of dielectric temperature spectrum, result shows the Curie temperature T of sample
cbe that 151 ℃, tripartite-Tetragonal temperature are T
rtit is 143 ℃.
Embodiment 7:
Adopt Bridgman-Stockbarge method for growing 0.06PSN-0.61PMN-0.33PT ferroelectric single crystal material.
Presoma ScNbO
4, MgNb
2o
6preparation with embodiment 6, take initial feed PbO, TiO according to the composition of 0.06PSN-0.61PMN-0.33PT
2with presoma ScNbO
4, MgNb
2o
6, wet ball grinding mixes it; The raw material mixing is packed in platinum crucible into platinum crucible used bottom crystal selector internal diameter 7mm, length/diameter=3.5, platinum crucible main part internal diameter 25mm; Platinum crucible is added a cover and is placed in crystal growing furnace, adopts falling crucible method to carry out crystal growth, 1400 ℃ of melt district furnace temperature, melt soaking time 24 hours, 28 ℃/cm of burner hearth axial-temperature gradient, dropping speed of the crucible 0.3mm/h; After growth finishes, treat that crystal furnace naturally cools to room temperature, peel off crucible and obtain the monocrystalline shown in Fig. 2, its size reaches 25mm × 30mm;
Obtained monocrystalline is cut to a small pieces grinding and be finely ground to powder for powder x-ray diffraction analysis, result as shown in Figure 3, shows that 0.06PSN-0.61PMN-0.33PT crystal is perovskite structure.
Obtained monocrystalline is cut to small pieces by (001) direction, section two sides is polished smooth with sand paper, the two sides then polishing smooth at it by silver electrode; Under the DC electric field of 10kV/cm to sample polarization 15 minutes; Place and after 24 hours, the sample polarizing is carried out to piezoelectric property test, measured piezoelectric constant d
33for 2571pC/N; After having surveyed piezoelectric constant, carry out the test of dielectric temperature spectrum, result as shown in Figure 4, shows the Curie temperature T of sample
cbe that 148 ℃, tripartite-Tetragonal temperature are T
rtbe 142 ℃, the specific inductivity under room temperature and dielectric loss are respectively 2412 and 0.01.
Obtained ferroelectric crystal material is cut to small pieces by (001) direction, section two sides is polished smooth with sand paper, the two sides then polishing smooth at it by silver electrode for the test of ferroelectric hysteresis loop.The ferroelectric hysteresis loop of measured (001) direction 0.06PSN-0.61PMN-0.33PT crystal cut as shown in Figure 4, shows, its coercive field E
cfor 4.043kV/cm, residual polarization P
rbe 44.54 μ C/cm2.
In addition, above detailed embodiment does not limit content of the present invention, as long as in technology of the present invention and Knowledge Scheme, makes corresponding modification or replacement, all should be in claim of the present invention.
Claims (8)
1. lead scandate columbate-PMN-PT ferro-electricity single crystal, is characterized in that: this materials chemistry formula is xPb (Sc
1/2nb
1/2) O
3-yPb (Mg
1/3nb
2/3) O
3-(1-x-y) PbTiO
3, wherein: 0.01≤x≤0.10,0.50≤y≤0.70,1-x-y ≠ 0, belongs to complex perovskite structure.
2. according to the lead scandate columbate-PMN-PT ferro-electricity single crystal described in claim 1, it is characterized in that: described x=0.02～0.08, y=0.58～0.68,1-x-y=0.32～0.34.
3. according to the lead scandate columbate-PMN-PT ferro-electricity single crystal described in claim 1, it is characterized in that: preferred ingredient is 0.06 Pb (Sc
1/2nb
1/2) O
3-0.61 Pb (Mg
1/3nb
2/3) O
3-0.33 PbTiO
3.
4. a method of preparing the lead scandate columbate-PMN-PT ferro-electricity single crystal described in claim 1, is characterized in that: comprise following concrete steps:
A) with the Nb of 99.9% above purity
2o
5and Sc
2o
3for initial feed is synthesized presoma ScNbO by solid reaction process
4; With the Nb of 99.9% above purity
2o
5and MgO, or Nb
2o
5and 4MgCO
3mg (OH)
24H
2o is that initial feed is synthesized presoma MgNb by solid reaction process
2o
6;
B) according to chemical formula xPb (Sc
1/2nb
1/2) O
3-yPb (Mg
1/3nb
2/3) O
3-(1-x-y) PbTiO
3composition take presoma ScNbO
4, presoma MgNb
2o
6, 99.99% above purity initial feed PbO(or Pb
3o
4) and the initial feed TiO of 99.99% above purity
2, carry out ball milling it mixed, wherein: 0.01≤x≤0.10,0.50≤y≤0.70,1-x-y ≠ 0;
C) raw material mixing is packed in platinum crucible, platinum crucible is added a cover and is placed in crystal growing furnace, adopt falling crucible method to carry out crystal growth, processing parameter comprises: 1350～1470 ℃ of melt district furnace temperature, melt soaking time 12～24 hours, 20～47 ℃/cm of burner hearth axial-temperature gradient, dropping speed of the crucible 0.1～1.5mm/h;
D) after growth finishes, treat that crystal furnace naturally cools to room temperature, peel off crucible and obtain monocrystalline.
5. the method for preparing lead scandate columbate-PMN-PT ferro-electricity single crystal described in claim 1 according to claim 4, is characterized in that: the ball milling in described step b) is dry ball milling or wet ball grinding Ball-milling Time 8～20 hours.
6. the method for preparing lead scandate columbate-PMN-PT ferro-electricity single crystal described in claim 1 according to claim 4, is characterized in that: the platiniferous purity of the platinum crucible in described step c) is not less than 99.9%.
7. the method for preparing lead scandate columbate-PMN-PT ferro-electricity single crystal described in claim 1 according to claim 4, it is characterized in that: the bottom of the platinum crucible in described step c) is provided with a cylindric crystal selector, and the length-to-diameter ratio of cylindric crystal selector is not less than 1.
8. a method of preparing the lead scandate columbate-PMN-PT ferro-electricity single crystal described in claim 1, is characterized in that: comprise following concrete steps:
A) with the Nb of 99.9% above purity
2o
5and Sc
2o
3for initial feed is synthesized presoma ScNbO by solid reaction process
4; With the Nb of 99.9% above purity
2o
5and MgO, or Nb
2o
5and 4MgCO
3mg (OH)
24H
2o is that initial feed is synthesized presoma MgNb by solid reaction process
2o
6;
B) according to chemical formula xPb (Sc
1/2nb
1/2) O
3-yPb (Mg
1/3nb
2/3) O
3-(1-x-y) PbTiO
3composition take presoma ScNbO
4, presoma MgNb
2o
6, 99.99% above purity initial feed PbO(or Pb
3o
4) and the initial feed TiO of 99.99% above purity
2, preparation crystal raw material, wherein: 0.01≤x≤0.10,0.50≤y≤0.70,1-x-y ≠ 0;
C) solubility promoter adopts PbO or the Pb of 99.99% above purity
3o
4, solubility promoter add-on is 50～80% of raw material total mass;
D) crystal raw material and solubility promoter mix through dry method or wet ball grinding, Ball-milling Time 8～20 hours;
E) raw material mixing is packed in platinum crucible, platinum crucible is added a cover and is placed on material in crystal growing furnace, 1200～1350 ℃ of material temperature, soaking time 12～24 hours;
F) after raw material fusing, carry out continuous Slow cooling, processing parameter comprises: it is material temperature that Slow cooling starts temperature, 1～15 ℃/day of Slow cooling speed, 900 ℃ of Slow cooling end temps;
G) Slow cooling cools to room temperature with the furnace after finishing, and falls solubility promoter with hot nitric acid dissolve, can obtain required monocrystalline.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410065657.6A CN103774228B (en) | 2014-02-26 | 2014-02-26 | Lead scandate columbate-PMN-PT ferro-electricity single crystal and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410065657.6A CN103774228B (en) | 2014-02-26 | 2014-02-26 | Lead scandate columbate-PMN-PT ferro-electricity single crystal and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103774228A true CN103774228A (en) | 2014-05-07 |
| CN103774228B CN103774228B (en) | 2016-05-18 |
Family
ID=50566962
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410065657.6A Active CN103774228B (en) | 2014-02-26 | 2014-02-26 | Lead scandate columbate-PMN-PT ferro-electricity single crystal and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103774228B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105154976A (en) * | 2015-09-28 | 2015-12-16 | 西安工业大学 | PSN-PMN-PT-PZ ferroelectric single-crystal material |
| CN105374931A (en) * | 2014-08-26 | 2016-03-02 | 中国科学院上海硅酸盐研究所 | Bi(Mg1/2Ti1/2)O3-PbTiO3(BMT-PT)-based high-temperature piezoelectric material and preparation method thereof |
| CN106637405A (en) * | 2015-10-30 | 2017-05-10 | 中国科学院福建物质结构研究所 | An infinitely mixable and meltable ferroelectric solid solution monocrystalline lead scandium niobate-lead magnesium niobate-lead titanate and a preparing method thereof |
| CN106954120A (en) * | 2016-12-21 | 2017-07-14 | 中国船舶重工集团公司第七〇五研究所 | A kind of low-frequency high-power transmitting transducer implementation method based on monocrystalline piezoelectric material |
| CN107190320A (en) * | 2017-05-26 | 2017-09-22 | 西安交通大学 | A kind of piezo-electric crystal raw material and preparation method thereof |
| CN110845230A (en) * | 2019-12-25 | 2020-02-28 | 西安工业大学 | Ternary-system lead scandium niobate-lead magnesium niobate-lead titanate ceramic and preparation method thereof |
| CN115094509A (en) * | 2022-07-22 | 2022-09-23 | 上海微逾新材料科技有限公司 | Lead zirconate titanate single crystal and preparation method and application thereof |
| CN117105663A (en) * | 2023-09-03 | 2023-11-24 | 森霸传感科技股份有限公司 | Low-temperature sintered ternary solid solution medium ceramic material and preparation method thereof |
-
2014
- 2014-02-26 CN CN201410065657.6A patent/CN103774228B/en active Active
Non-Patent Citations (3)
| Title |
|---|
| YIPING 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", 《JOURNAL OF CRYSTAL GROWTH》, vol. 226, 30 June 2001 (2001-06-30), pages 111 - 116, XP004242499, DOI: doi:10.1016/S0022-0248(01)01362-8 * |
| 尹珂: "弛豫铁电晶体和反铁电晶体的生长和表征", 《西安工业大学学位论文》, 31 March 2008 (2008-03-31) * |
| 田瑞英: "PSN-PMN-PT铁电晶体的生长、结构和性能", 《中国硕士学位论文全文数据库 工程科技I辑》, no. 7, 15 July 2013 (2013-07-15) * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105374931A (en) * | 2014-08-26 | 2016-03-02 | 中国科学院上海硅酸盐研究所 | Bi(Mg1/2Ti1/2)O3-PbTiO3(BMT-PT)-based high-temperature piezoelectric material and preparation method thereof |
| CN105374931B (en) * | 2014-08-26 | 2018-05-08 | 中国科学院上海硅酸盐研究所 | Titanium magnesium acid bismuth-lead titanate high-temperature piezoelectric material and preparation method thereof |
| CN105154976A (en) * | 2015-09-28 | 2015-12-16 | 西安工业大学 | PSN-PMN-PT-PZ ferroelectric single-crystal material |
| CN105154976B (en) * | 2015-09-28 | 2017-12-19 | 西安工业大学 | A kind of lead scandate columbate lead magnesio-niobate lead zirconium titanate lead plumbate ferroelectric single crystal material |
| CN106637405A (en) * | 2015-10-30 | 2017-05-10 | 中国科学院福建物质结构研究所 | An infinitely mixable and meltable ferroelectric solid solution monocrystalline lead scandium niobate-lead magnesium niobate-lead titanate and a preparing method thereof |
| CN106637405B (en) * | 2015-10-30 | 2019-04-16 | 中国科学院福建物质结构研究所 | Ferroelectric sosoloid monocrystalline lead scandate columbate-lead magnesium niobate-lead titanate and preparation method thereof of unlimited consolute |
| CN106954120A (en) * | 2016-12-21 | 2017-07-14 | 中国船舶重工集团公司第七〇五研究所 | A kind of low-frequency high-power transmitting transducer implementation method based on monocrystalline piezoelectric material |
| CN106954120B (en) * | 2016-12-21 | 2019-07-05 | 中国船舶重工集团公司第七一五研究所 | A kind of low-frequency high-power transmitting transducer implementation method based on monocrystalline piezoelectric material |
| CN107190320A (en) * | 2017-05-26 | 2017-09-22 | 西安交通大学 | A kind of piezo-electric crystal raw material and preparation method thereof |
| CN110845230A (en) * | 2019-12-25 | 2020-02-28 | 西安工业大学 | Ternary-system lead scandium niobate-lead magnesium niobate-lead titanate ceramic and preparation method thereof |
| CN115094509A (en) * | 2022-07-22 | 2022-09-23 | 上海微逾新材料科技有限公司 | Lead zirconate titanate single crystal and preparation method and application thereof |
| CN117105663A (en) * | 2023-09-03 | 2023-11-24 | 森霸传感科技股份有限公司 | Low-temperature sintered ternary solid solution medium ceramic material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103774228B (en) | 2016-05-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103774228A (en) | Lead scandium niobate-lead magnesium diniobate-lead titanate ferroelectric monocrystal and preparation method thereof | |
| Moriana et al. | Lead-free textured piezoceramics using tape casting: A review | |
| US7972527B2 (en) | Method of making ternary piezoelectric crystals | |
| Guo et al. | Peculiar properties of a high Curie temperature Pb (In1/2Nb1/2) O3–PbTiO3 single crystal grown by the modified Bridgman technique | |
| CN101985775A (en) | Ternary system relaxation ferroelectric single crystal material and preparation method thereof | |
| CN102051685A (en) | Novel ferroelectric single-crystal lead ytterbium niobate-lead magnesium niobate-lead titanate | |
| CN104419984B (en) | Preparation method of perovskite-structure relaxor ferroelectric single crystal lead indium niobate-lead magnesium niobate-lead titanate | |
| KR102698322B1 (en) | Polar nano-stationary engineering-relaxed-PbTiO3 ferroelectric crystals | |
| CN103172373A (en) | Ternary ferroelectric solid solution lead niobate ytterbate-lead zinc niobate-lead titanate | |
| CN102560617A (en) | Method for preparing ferroelectric single crystal lead indium niobate-lead titanate | |
| CN103360068A (en) | Manganese antimony-doped lead zirconate titanate piezoelectric ceramic | |
| CN106637405B (en) | Ferroelectric sosoloid monocrystalline lead scandate columbate-lead magnesium niobate-lead titanate and preparation method thereof of unlimited consolute | |
| CN1187483C (en) | Melt method for growing sosoloid monocrystal of lead lead-titanate niobium-zincate | |
| CN105036736A (en) | Sodium-bismuth-titanate-base lead-free electrostrictive ceramic material and preparation method thereof | |
| CN102644114A (en) | Ferroelectric monocrystal lead lutecium niobate-lead titanate and preparation method thereof | |
| CN1196817C (en) | Growth of high curie point lead niobate lead indate-lead titanate single crystal using crucible descending method | |
| CN109957837A (en) | A kind of neodymium doping lead magnesium niobate-lead titanate material and preparation method thereof | |
| US8597535B2 (en) | Method of making ternary piezoelectric crystals | |
| CN103046138A (en) | Ferroelectric monocrystal lead ferrite niobate-lead ytterbium niobate-lead titanate and preparation method thereof | |
| CN105154976B (en) | A kind of lead scandate columbate lead magnesio-niobate lead zirconium titanate lead plumbate ferroelectric single crystal material | |
| Zhao et al. | Improvement in synthesis of (K 0.5 Na 0.5) NbO 3 powders by Ge 4+ acceptor doping | |
| CN103710754A (en) | Ferroelectric piezoelectric single crystal lead holmium niobate-lead magnesium niobate-lead titanate as well as preparation and application thereof | |
| CN103469307A (en) | Tetragonal phase lithium-antimony-tantalum co-doped potassium niobate sodium-based piezoelectric crystal and preparation method thereof | |
| Ichinose et al. | Dielectric and piezoelectric properties of Pb (Sc1/2Nb1/2) O3–Pb (Ni1/3Nb2/3) O3–PbTiO3 ternary ceramic materials | |
| Spann et al. | Development of textured antimony sulphoiodide |
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 |