CN105374931A - Bi(Mg1/2Ti1/2)O3-PbTiO3(BMT-PT)-based high-temperature piezoelectric material and preparation method thereof - Google Patents
Bi(Mg1/2Ti1/2)O3-PbTiO3(BMT-PT)-based high-temperature piezoelectric material and preparation method thereof Download PDFInfo
- Publication number
- CN105374931A CN105374931A CN201410424420.2A CN201410424420A CN105374931A CN 105374931 A CN105374931 A CN 105374931A CN 201410424420 A CN201410424420 A CN 201410424420A CN 105374931 A CN105374931 A CN 105374931A
- Authority
- CN
- China
- Prior art keywords
- temperature
- acid bismuth
- piezoelectric material
- titanium magnesium
- crystal
- 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
Landscapes
- Compositions Of Oxide Ceramics (AREA)
Abstract
The present invention relates to a Bi(Mg1/2Ti1/2)O3-PbTiO3(BMT-PT)-based high-temperature piezoelectric material and a preparation method thereof. The Bi(Mg1/2Ti1/2)O3-PbTiO3(BMT-PT)-based high-temperature piezoelectric material has a ABO3 perovskite-type composite oxide structure, a formed formula is (1-x) Bi (Mg1/2Ti1/2)O3-xPbTiO3+yA2Oa+zB2Ob, wherein x is larger than 0.50 and is smaller than 1, the element A is an A-site doping element in ABO3, the element B is a B-site doping element in ABO3, y is larger than or equal to 0 and is smaller than or equal to 5mol%, z is larger than or equal to 0 and is smaller than or equal to 10mol%, and y+z is smaller than or equal to 10mol%.
Description
Technical field
The invention belongs to piezoelectric monocrystal growing technology field, be specifically related to a kind of titanium magnesium acid bismuth-lead titanate high-temperature piezoelectric material and preparation method thereof.
Background technology
Piezoelectric is a kind of very important functional material, the mutual conversion that it can realize between electric energy and mechanical energy by forward and inverse piezoelectric effect.Due to performances such as the dielectric of its uniqueness, piezoelectricity, ferroelectric, pyroelectricities, have a wide range of applications in numerous high sharp technical fields such as military affairs, Aero-Space, geological prospecting, medical treatment, communications.Along with electronic technology and computer-controlled high speed development, in some special dimension, need the high accuracy driver of steady operation in high-temperature severe environment, detection transducer and sensor piezoelectric device.And not only need at a higher temperature as high-temperature piezoelectric material, not recurring structure phase transformation, there is not high temperature depolarization phenomenon, more need it to have piezoelectricity and dielectric property do not vary with temperature and produce the high-temperature stability of fluctuation.
The piezoelectric be most widely used at present is PZT sill, there is tripartite/Tetragonal coexistence and accurate homotype phase battery limit (BL) (MPB) in this system.But its working temperature can only be limited in Curie temperature (T
c) half about, greatly about 150 DEG C.In recent years along with people are more and more higher to PZT (piezoelectric transducer) operating temperature requirements, the research application of high-temperature piezoelectric material becomes a study hotspot gradually.Such as, the Ultrasonic Well Logging transducer used under oil well just needs to be operated in the temperature environment of 200-300 DEG C.Traditional Pb (Zr, Ti) O
3(PZT) there is ferroelectric-para-electric phase transformation at this temperature in piezoelectric ceramic, and cisco unity malfunction.Therefore, Curie temperature is studied high and the novel piezoelectric material that piezoelectric property is excellent is one of vital task of 21 century material supply section scholar.
The piezoelectric of what current research was more have high-curie temperature perovskite structure mainly contains the binary system solid-solution materials such as scandium acid bismuth-lead titanates (BS-PT), zirconium zincic acid bismuth-lead titanates (BZZ-PT), bismuth ferrite-lead titanates (BF-PT) and titanium magnesium acid bismuth-lead titanates (BMT-PT).Although scandium acid bismuth-lead titanates (BS-PT) has higher Curie temperature and piezoelectric property, but its raw material Sc
2o
3expensive, make the cost performance of material low, be difficult to obtain large-scale industrialization application; And zirconium zincic acid bismuth-lead titanates (BZZ-PT) is though Curie temperature can reach more than 600 DEG C, so its piezoelectric property is too low, greatly limit its use; Bismuth ferrite-lead titanates (BF-PT) is comparatively large due to its leakage current, is difficult to abundant polarization, makes its piezoelectric property too low and limits its application.
Titanium magnesium acid bismuth-lead titanates (BMT-PT) has higher Curie temperature and good piezoelectric property, and cost is low, and lead tolerance is few, meets the requirement of modern society's sustainable development, has good Research Prospects.Regrettably yet there are no the performance of titanium magnesium acid bismuth-lead titanates (BMT-PT) high-temperature piezoelectric monocrystalline and the bibliographical information of preparation technology in existing document.The perovskite structure poor stability of titanium magnesium acid bismuth-lead titanates (BMT-PT) itself, which increases the growth difficulty of titanium magnesium acid bismuth-lead titanates (BMT-PT) crystal.
Summary of the invention
The present invention is intended to overcome the not good and preparation defect not easily of existing titanium magnesium acid bismuth-lead titanates high-temperature piezoelectric material performance, the invention provides a kind of titanium magnesium acid bismuth-lead titanate high-temperature piezoelectric material and preparation method thereof.
The invention provides a kind of titanium magnesium acid bismuth-lead titanate high-temperature piezoelectric material, described titanium magnesium acid bismuth-lead titanate high-temperature piezoelectric material has ABO
3perovskite composite oxide structure, the chemical formula of composition is (1-x) Bi (Mg
1/2ti
1/2) O
3-xPbTiO
3+ yA
2o
a+ zB
2o
b, wherein 0.50<x<1, elements A is ABO
3middle A position doped chemical, is selected from Li
+, Na
+, K
+, Ba
2+, Sr
2+, Ca
2+, and La
3+in at least one, element B is ABO
3middle B position doped chemical, is selected from Zn
2+, Ni
2+, Mn
2+, Sc
3+, Fe
3+, In
3+, Ga
3+, Co
3+, Cr
3+, Mn
3+, Mn
4+, Zr
4+, Nb
5+, Ta
5+, Sb
5+, V
5+, and W
6+in at least one, a is the doping valence state of elements A, and b is the doping valence state of element B, 0≤y≤5mol%, 0≤z≤10mol%, and y+z≤10mol%.
Preferably, 0.5 < x≤0.70.
Preferably, the working temperature interval of described titanium magnesium acid bismuth-lead titanate high-temperature piezoelectric material is room temperature-600 DEG C, the dielectric constant 40F/m-180000F/m in working temperature interval.
Again, the invention provides a kind of preparation method of above-mentioned titanium magnesium acid bismuth-lead titanate high-temperature piezoelectric material, described method comprises:
1) according to the mol ratio in the chemical formula of described titanium magnesium acid bismuth-lead titanate high-temperature piezoelectric material between metallic element, take metal oxide powder as material powder, wherein, the oxide of Bi is Bi
2o
3, the oxide of Mg is the oxide of MgO, Ti is TiO
2, the oxide of Pb is PbO and/or Pb
3o
4;
2) flux into material powder quality 20-90% is taken, with material powder Homogeneous phase mixing, obtain preparing rising of described titanium magnesium acid bismuth-lead titanate high-temperature piezoelectric material to expect, wherein flux be lead oxide, lead orthoplumbate, lead fluoride, bismuth oxide, at least one of fluoridizing in bismuth, boron oxide, sodium chloride, potassium chloride;
3) by step 2) prepare rise expect, successively through isothermal holding and cooling process, obtain described titanium magnesium acid bismuth-lead titanate high-temperature piezoelectric material crystal boule, wherein, the parameter of isothermal holding is: 1100-1300 DEG C insulation 2-20 hour; Cooling is treated to, and is cooled to room temperature with the speed of 0.5-200 DEG C/h;
4) by step 3) crystal boule prepared carries out pickling, obtains described titanium magnesium acid bismuth-lead titanate high-temperature piezoelectric material.
Preferably, step 2) in, flux is material powder quality 20-60%.
Preferably, step 3) in, first expect described in the platinum crucible be sealed in, then be placed in alumina crucible and carry out the process that is incubated and lowers the temperature, wherein, described platinum crucible has 1 layer, 2 layers or 3 layers, and the thickness of every one deck is 0.1-0.2mm.
Preferably, step 3) in, heating mode in isothermal holding process is: after being first warming up to 700-1000 DEG C through 2-10 hours, be incubated 2-20 hour (preferred 2-12 hour), be warming up to through 2-5 hours again isothermal holding temperature 1100-1300 DEG C (preferred 1150-1300 DEG C), be incubated 2-20 hour (preferred 2-12 hour).
Preferably, step 3) in, described isothermal holding and cooling process are carried out in Muffle furnace, and cooling is treated to: be first cooled to 950-1050 DEG C with 0.5-100 DEG C/h, then be cooled to room temperature.
Preferably, step 3) in, described isothermal holding and cooling process are carried out in crystal growing furnace, cooling is treated to: by rising to expect and to decline with the speed of 0.1-1.2mm/ hour through second time isothermal holding, 1100-1300 DEG C of high-temperature regions in crystal growing furnace and the length between 800-1000 DEG C of low-temperature spaces are the temperature gradient field of 50-100mm, then are cooled to room temperature.
Preferably, step 4) in, adopt acetic acid to carry out acidity.
Beneficial effect of the present invention:
The present invention's titanium magnesium that adopted o to prepare acid bismuth-lead titanates (BMT-PT) base high-temperature piezoelectric monocrystalline, advantage is: 1, crystal growth temperature is low, can obtain pure perovskite phase crystal; 2, the requirement of low-temperature epitaxy process to growth instrument is low; 3, material powder is contained in crucible and can seals easily; And due to growth temperature lower, the volatilization of raw material is less, can control the component of institute's grown crystal better, prevent component deviation etc.Utilizing method of the present invention to grow titanium magnesium acid bismuth-lead titanates (BMT-PT) base high-temperature piezoelectric monocrystalline is pure perovskite structure, produces, and have very high Curie temperature (668 DEG C) and good piezoelectric property without dephasign.
Accompanying drawing explanation
Fig. 1 shows the x-ray diffractogram of powder of titanium magnesium acid bismuth-lead titanates (BMT-PT) the high-temperature piezoelectric monocrystalline prepared in an embodiment of the invention;
Fig. 2 shows Jie's temperature curve chart of the dielectric constant with temperature change of titanium magnesium acid bismuth-lead titanates (BMT-PT) high-temperature piezoelectric single-crystal wafer in an embodiment of the invention.
Embodiment
Further illustrate the present invention below in conjunction with accompanying drawing and following execution mode, should be understood that accompanying drawing and following execution mode are only for illustration of the present invention, and unrestricted the present invention.
The invention discloses a kind of high-curie temperature titanium magnesium acid bismuth-lead titanates (BMT-PT) base piezoelectric and o growing method thereof, belong to field of crystal growth.The chemical formula of described titanium magnesium acid bismuth-lead titanate high-temperature piezoelectric material is (1-x) Bi (Mg
1/2ti
1/2) O
3-xPbTiO
3, be abbreviated as (1-x) BMT-xPT, wherein x represents PbTiO
3the molar fraction of component, 0.50<x<1, its structure is ABO
3perovskite structure.Wherein, the Li of 0 ~ 5mol% can also be mixed in A position
+, Na
+, K
+, Ba
2+, Sr
2+, Ca
2+, La
3+plasma or ion population, preferred Li
+, Ba
2+, La
3+; The Zn of 0 ~ 10mol% is mixed in B position
2+, Ni
2+, Mn
2+, Sc
3+, Fe
3+, In
3+, Ga
3+, Co
3+, Cr
3+, Mn
3+, Mn
4+, Zr
4+, Nb
5+, Ta
5+, Sb
5+, V
5+, W
6+plasma or ion population, preferred Cr
3+, Mn
4+, Zr
4+, Nb
5+, performance is optimized it.Described method comprises flux growth method and flux Bridgman method, and growth step comprises Feedstock treating, intensification fusing, grows and a series of single crystal growth process of lowering the temperature.
(1-x) Bi (Mg that the present invention adopts o to grow
1/2ti
1/2) O
3-xPbTiO
3material is pure perovskite structure (ABO3), and produce without dephasign, Curie temperature is up to 668 DEG C.The advantage of the inventive method: 1, crucible is salable, volatilization is few, and temperature required lower, the cycle is shorter; 2, simple to operate, growth course is easy to sequencing, automation; 3, production efficiency and rate of finished products higher, be easy to suitability for industrialized production.
Preferably, 0.50<x≤0.70.
The described titanium magnesium acid bismuth-lead titanate piezoelectric prepared in an embodiment of the invention is of a size of 2 ~ 50mm.Preferably, described titanium magnesium acid bismuth-lead titanate piezoelectric is of a size of 10 ~ 20mm.
The o growing method of described titanium magnesium acid bismuth-lead titanate high-temperature piezoelectric material, described method specifically comprises the steps:
Step one, according to (1-x) Bi (Mg
1/2ti
1/2) O
3-xPbTiO
3stoichiometric proportion accurately takes Bi
2o
3, MgO, TiO
2and Pb
3o
4material powder;
Step 2, take and account for material powder 20-90%, the preferably flux of 20% ~ 60%, and mix with material powder crystal growth rises and expects; Flux is PbO, PbF
2, Bi
2o
3, BiF
3, B
2o
3, NaCl and/or KCl;
Step 3, will rise to expect and put into crucible and seal, crucible will be placed in stove;
Step 4, crucible is at 700 ~ 1000 DEG C of insulation 2 ~ 20h, then raised temperature to 1100 ~ 1300 DEG C, insulation 2 ~ 20h has made to expect and has all melted (preferably melt raw material in 1150 ~ 1300 DEG C of temperature ranges), temperature-fall period is: in-furnace temperature declines with the speed of 0.1 ~ 1.2mm/h with the speed cool to room temperature of 0.5 ~ 200 DEG C/h or crucible, temperature gradient field in crystal growing furnace between high-temperature region and low-temperature space, melt gradually crystalline growth becomes crystal, grow complete, crystal growth in-furnace temperature is with the speed cool to room temperature of 10 ~ 200 DEG C/h, crystal is come out of the stove,
Step 5, carefully peel off crucible, take out crystal boule, after pickling processes, obtain titanium magnesium acid bismuth-lead titanates (BMT-PT) base high-temperature piezoelectric material.
In step one, also MnO can be taken
2, Cr
2o
3, Nb
2o
5, Li
2o, La
2o
3and/or BaO, the amount taking this material is no more than 10% of the molar fraction of total inventory.
The Bi taken
2o
3, MgO, TiO
2and Pb
3o
4the purity of material powder is greater than 99.99%.Pb wherein
3o
4can with PbO or PbO and Pb
3o
4combination replace.
Described method is flux growth method, and wherein, step 3, will rise expects puts into crucible, then crucible is put into alumina crucible, and then is placed in Muffle furnace.
Described method is flux Bridgman method, and wherein, step 3, will rise expects puts into crucible, then crucible is put into ceramic skirt, and then is placed in crystal growing furnace.Described skirt is alumina ceramic tube.
Step 3, crucible used is platinum crucible, and adopts the individual layer of sealing or double-deck or three-decker, and every layer thickness is 0.1 ~ 0.2mm.
Step 4, stove (Muffle furnace) interior temperature from ambient rises to 700 ~ 1000 DEG C through 2 ~ 10h (preferred 2-8h), and be incubated 2 ~ 12h (preferred 2-10h), 1150 ~ 1300 DEG C are risen to again through 2 ~ 5h (preferred 2-4h), insulation 2 ~ 12h (more preferably 3-12h), last in-furnace temperature is cooled to room temperature with the speed of 0.5 ~ 100 DEG C/h.
Step 4, stove (crystal growing furnace) interior temperature from ambient rises to 700 ~ 1000 DEG C through 2 ~ 10h (preferred 2-8h), and be incubated 2 ~ 12h (preferred 2-10h), 1150 ~ 1300 DEG C are risen to again through 2 ~ 5h (preferred 2-4h), insulation 2 ~ 12h (more preferably 3-12h), then crucible declines with the speed of 0.1 ~ 1.2mm/h, temperature gradient field in crystal growing furnace between high-temperature region and low-temperature space, melt gradually crystalline growth becomes crystal, grow complete, crystal growth in-furnace temperature is with the speed cool to room temperature of 10 ~ 200 DEG C/h.
Described flux comprises lead oxide, lead fluoride, bismuth oxide, fluoridizes bismuth, boron oxide, sodium chloride, one of potassium chloride or its combination in any.Such as flux can be: PbO, PbF
2, Bi
2o
3or their combination etc.PbO in flux also can use Pb
3o
4all or part of alternative.
The o growing method of described titanium magnesium acid bismuth-lead titanate high-temperature piezoelectric material, also comprises step 6 further, by solvent clean titanium magnesium acid bismuth-lead titanates (BMT-PT) base high-temperature piezoelectric material.
Described solvent is deionized water, alcohol or inorganic weak acid.
The object of the invention is the deficiency for existing piezoelectric suitable application area, a kind of titanium magnesium acid bismuth-lead titanates (BMT-PT) base high-temperature piezoelectric material is provided;
Another object of the present invention is to provide a kind of method growing high-temperature piezoelectric material of the present invention, described method is o, comprises flux growth method and flux Bridgman method.By adding a certain amount of flux, significantly can reduce the temperature needed for crystal growth, thus realize BMT-PT crystal complete growth under heat decomposition temperature.
In the present invention, crystal growth temperature is 1150 ~ 1300 DEG C.
The present invention has adopted o legal system for titanium magnesium acid bismuth-lead titanates (BMT-PT) base high-temperature piezoelectric monocrystalline, and advantage is: 1, crystal growth temperature is low, can obtain pure perovskite phase crystal; 2, the requirement of low-temperature epitaxy process to growth instrument is low; 3, material powder is contained in crucible and can seals easily, and due to growth temperature lower, the volatilization of raw material is less, can control the component of institute's grown crystal better, prevent component deviation etc.Utilizing method of the present invention to grow titanium magnesium acid bismuth-lead titanates (BMT-PT) base high-temperature piezoelectric monocrystalline is pure perovskite structure, produces, and have very high Curie temperature (668 DEG C) and good piezoelectric property without dephasign.
Below some exemplary embodiments are listed further better the present invention to be described.Should understand; the above-mentioned execution mode that the present invention describes in detail; and following examples are only not used in for illustration of the present invention and limit the scope of the invention, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention.In addition, concrete proportioning, time, temperature etc. in following technological parameter are also only exemplary, and those skilled in the art can select suitable value in the scope of above-mentioned restriction.
Embodiment 1
One, by chemical formula 0.49Bi (Mg
1/2ti
1/2) O
3-0.51PbTiO
3stoichiometric proportion take PbO, Bi
2o
3, MgO and TiO
2material powder;
Two, take account for raw material gross weight 30% PbO as flux, fully mix obtain crystal growth with rise expect;
Three, will rise to expect and load in platinum crucible and seal, the platinum crucible of good seal is putting into alumina crucible, is then placed in Muffle furnace;
Four, in Muffle furnace, temperature from ambient is warming up to 1000 DEG C through 4h and is incubated 6h, then after 3h is warming up to 1200 DEG C, is incubated 4h, and in Muffle furnace, temperature is cooled to room temperature with the speed of 6 DEG C/h subsequently;
Five, crystal growth completes, and crystal is come out of the stove, and carefully peels off crucible, takes out crystal;
Six, crystal boule acetic acid is soaked to remove flux PbO, then after deionized water washing, namely obtain titanium magnesium acid bismuth-lead titanates high-temperature piezoelectric monocrystalline;
From Fig. 1, can find out, the titanium magnesium acid bismuth-lead titanate monocrystal grown out is pure Tetragonal perovskite structure;
From Fig. 2, can find out, the working temperature interval of the titanium magnesium acid bismuth-lead titanate high-temperature piezoelectric material prepared in the present embodiment is room temperature-600 DEG C, the dielectric constant 180F/m-176000F/m in working temperature interval.
Embodiment 2
One, by chemical formula 0.45Bi (Mg
1/2ti
1/2) O
3-0.55PbTiO
3stoichiometric proportion take Bi
2o
3, MgO, TiO
2and Pb
3o
4material powder;
Two, the PbF accounting for raw material gross weight 40% is taken
2as flux, fully mix obtain crystal growth with rise expect;
Three, will rise to expect and load in platinum crucible and seal, the platinum crucible of good seal is putting into alumina crucible, is then placed in Muffle furnace;
Four, in Muffle furnace, temperature from ambient is warming up to 900 DEG C through 4h and is incubated 3h, then after 4h is warming up to 1180 DEG C, is incubated 4h, and in Muffle furnace, temperature is cooled to room temperature with the speed of 10 DEG C/h subsequently;
Five, crystal growth completes, and crystal is come out of the stove, and carefully peels off crucible, takes out crystal;
Six, crystal boule acetic acid is soaked to remove flux PbF
2, then after deionized water washing, namely obtain titanium magnesium acid bismuth-lead titanates high-temperature piezoelectric monocrystalline;
The working temperature interval of the titanium magnesium acid bismuth-lead titanate high-temperature piezoelectric material prepared in the present embodiment is room temperature-580 DEG C, the dielectric constant 160F/m-160000F/m in working temperature interval.
Embodiment 3
One, by chemical formula 0.40Bi (Mg
1/2ti
1/2) O
3-0.60PbTiO
3stoichiometric proportion take Bi
2o
3, MgO, TiO
2and Pb
3o
4material powder;
Two, PbO and PbF accounting for raw material gross weight 50% is taken
2as flux, fully mix obtain crystal growth with rise expect;
Three, will rise to expect and load in platinum crucible and seal, the platinum crucible of good seal is putting into alumina crucible, is then placed in Muffle furnace;
Four, in Muffle furnace, temperature from ambient is warming up to 900 DEG C through 6h and is incubated 4h, then after 5h is warming up to 1250 DEG C, is incubated 5h, and in Muffle furnace, temperature is cooled to room temperature with the speed of 15 DEG C/h subsequently;
Five, crystal growth completes, and crystal is come out of the stove, and carefully peels off crucible, takes out crystal;
Six, crystal boule acetic acid is soaked to remove flux PbO and PbF
2, then after deionized water washing, namely obtain titanium magnesium acid bismuth-lead titanates high-temperature piezoelectric monocrystalline;
The working temperature interval of the titanium magnesium acid bismuth-lead titanate high-temperature piezoelectric material prepared in the present embodiment is room temperature-570 DEG C, the dielectric constant 130F/m-152000F/m in working temperature interval.
Embodiment 4
One, by chemical formula 0.30Bi (Mg
1/2ti
1/2) O
3-0.70PbTiO
3stoichiometric proportion take Bi
2o
3, MgO, TiO
2and Pb
3o
4material powder;
Two, PbO and B accounting for raw material gross weight 20% is taken
2o
3as flux, fully mix obtain crystal growth with rise expect;
Three, will rise to expect and load in platinum crucible and seal, the platinum crucible of good seal is putting into alumina crucible, is then placed in Muffle furnace;
Four, in Muffle furnace, temperature from ambient is warming up to 1000 DEG C through 6h and is incubated 6h, then after 4h is warming up to 1200 DEG C, is incubated 4h, and in Muffle furnace, temperature is down to 1050 DEG C with the speed of 1 DEG C/h subsequently, then naturally cools to room temperature;
Five, crystal growth completes, and crystal is come out of the stove, and carefully peels off crucible, takes out crystal;
Six, crystal boule acetic acid is soaked to remove flux PbO and B
2o
3, then after deionized water washing, namely obtain titanium magnesium acid bismuth-lead titanates high-temperature piezoelectric monocrystalline;
The working temperature interval of the titanium magnesium acid bismuth-lead titanate high-temperature piezoelectric material prepared in the present embodiment is room temperature-550 DEG C, the dielectric constant 100F/m-130000F/m in working temperature interval.
Embodiment 5
One, by chemical formula 0.20Bi (Mg
1/2ti
1/2) O
3-0.80PbTiO
3stoichiometric proportion take Bi
2o
3, MgO, TiO
2and Pb
3o
4material powder;
Two, the PbF accounting for raw material gross weight 30% is taken
2and B
2o
3as flux, fully mix obtain crystal growth with rise expect;
Three, will rise to expect and load in platinum crucible and seal, the platinum crucible of good seal is putting into alumina crucible, is then placed in Muffle furnace;
Four, in Muffle furnace, temperature from ambient is warming up to 800 DEG C through 4h and is incubated 6h, then after 4h is warming up to 1300 DEG C, is incubated 6h, and in Muffle furnace, temperature is down to 1000 DEG C with the speed of 0.8 DEG C/h subsequently, then naturally cools to room temperature;
Five, crystal growth completes, and crystal is come out of the stove, and carefully peels off crucible, takes out crystal;
Six, crystal boule acetic acid is soaked to remove flux PbF
2and B
2o
3, then after deionized water washing, namely obtain titanium magnesium acid bismuth-lead titanates high-temperature piezoelectric monocrystalline;
The working temperature interval of the titanium magnesium acid bismuth-lead titanate high-temperature piezoelectric material prepared in the present embodiment is room temperature-535 DEG C, the dielectric constant 80F/m-115000F/m in working temperature interval.
Embodiment 6
One, by chemical formula 0.10Bi (Mg
1/2ti
1/2) O
3-0.90PbTiO
3stoichiometric proportion take Bi
2o
3, MgO, TiO
2and Pb
3o
4material powder;
Two, the PbF accounting for raw material gross weight 40% is taken
2and BiF
3as flux, fully mix obtain crystal growth with rise expect;
Three, will rise to expect and load in platinum crucible and seal, the platinum crucible of good seal is putting into alumina crucible, is then placed in Muffle furnace;
Four, in Muffle furnace, temperature from ambient is warming up to 1000 DEG C through 6h and is incubated 3h, then after 4.5h is warming up to 1300 DEG C, is incubated 8h, and in Muffle furnace, temperature is cooled to room temperature with the speed of 20 DEG C/h subsequently;
Five, crystal growth completes, and crystal is come out of the stove, and carefully peels off crucible, takes out crystal;
Six, crystal boule acetic acid is soaked to remove flux PbF
2and BiF
3, then after deionized water washing, namely obtain titanium magnesium acid bismuth-lead titanates high-temperature piezoelectric monocrystalline;
The working temperature interval of the titanium magnesium acid bismuth-lead titanate high-temperature piezoelectric material prepared in the present embodiment is room temperature-520 DEG C, the dielectric constant 40F/m-95000F/m in working temperature interval.
Embodiment 7
One, by chemical formula 0.40Bi (Mg
1/2ti
1/2) O
3-0.60PbTiO
3stoichiometric proportion take Bi
2o
3, MgO, TiO
2and Pb
3o
4material powder;
Two, take account for raw material gross weight 60% NaCl and KCl as flux, fully mix obtain crystal growth with rise expect;
Three, will rise to expect and load in platinum crucible and seal, the platinum crucible of good seal is putting into alumina crucible, is then placed in Muffle furnace;
Four, in Muffle furnace, temperature from ambient is warming up to 700 DEG C through 6h and is incubated 5h, then after 5h is warming up to 1230 DEG C, is incubated 5h, and in Muffle furnace, temperature is cooled to room temperature with the speed of 10 DEG C/h subsequently;
Five, crystal growth completes, and crystal is come out of the stove, and carefully peels off crucible, takes out crystal;
Six, crystal boule is soaked in water remove flux NaCl and KCl, then after deionized water washing, namely obtains titanium magnesium acid bismuth-lead titanates high-temperature piezoelectric monocrystalline;
The working temperature interval of the titanium magnesium acid bismuth-lead titanate high-temperature piezoelectric material prepared in the present embodiment is room temperature-565 DEG C, the dielectric constant 140F/m-160000F/m in working temperature interval.
Embodiment 8
One, by chemical formula 0.20Bi (Mg
1/2ti
1/2) O
3-0.80PbTiO
3stoichiometric proportion take Bi
2o
3, MgO, TiO
2and Pb
3o
4material powder;
Two, take account for raw material gross weight 30% PbO as flux, fully mix obtain crystal growth with rise expect;
Three, will rise to expect and load in platinum crucible and seal, the platinum crucible of good seal loads in skirt, and then is placed in crystal growing furnace;
Four, crucible is warming up to 700 DEG C through 2h, and be incubated 2h, then 1250 DEG C are warming up to through 2h, and be incubated 3h, raw material is all melted, then crucible declines with the speed of 0.1mm/h, the temperature gradient field in crystal growing furnace between high-temperature region and low-temperature space, and melt gradually crystalline growth becomes crystal; Grow complete, the speed of crucible 10 DEG C/h is cooled to room temperature, and crystal is come out of the stove;
Five, crystal growth completes, and crystal is come out of the stove, and carefully peels off crucible, takes out crystal;
Six, crystal boule acetic acid is soaked to remove flux PbO, then after deionized water washing, namely obtain titanium magnesium acid bismuth-lead titanates high-temperature piezoelectric monocrystalline;
The working temperature interval of the titanium magnesium acid bismuth-lead titanate high-temperature piezoelectric material prepared in the present embodiment is room temperature-530 DEG C, the dielectric constant 100F/m-120000F/m in working temperature interval.
Embodiment 9
One, by chemical formula 0.35Bi (Mg
1/2ti
1/2) O
3-0.65PbTiO
3stoichiometric proportion take Bi
2o
3, MgO, TiO
2and Pb
3o
4material powder;
Two, PbO, PbF of accounting for raw material gross weight 30% is taken
2and B
2o
3as flux, fully mix obtain crystal growth with rise expect;
Three, will rise to expect and load in platinum crucible and seal, the platinum crucible of good seal loads in skirt, and then is placed in crystal growing furnace;
Four, crucible is warming up to 800 DEG C through 4h, and be incubated 4h, then 1300 DEG C are warming up to through 4h, and be incubated 6h, raw material is all melted, then crucible declines with the speed of 0.5mm/h, the temperature gradient field in crystal growing furnace between high-temperature region and low-temperature space, and melt gradually crystalline growth becomes crystal; Grow complete, the speed of crucible 50 DEG C/h is cooled to room temperature, and crystal is come out of the stove;
Five, crystal growth completes, and crystal is come out of the stove, and carefully peels off crucible, takes out crystal;
Six, crystal boule acetic acid is soaked to remove flux PbO etc., then after deionized water washing, namely obtain titanium magnesium acid bismuth-lead titanates high-temperature piezoelectric monocrystalline;
The working temperature interval of the titanium magnesium acid bismuth-lead titanate high-temperature piezoelectric material prepared in the present embodiment is room temperature-570 DEG C, the dielectric constant 130F/m-155000F/m in working temperature interval.
Embodiment 10
One, by chemical formula 0.30Bi (Mg
1/2ti
1/2) O
3-0.70PbTiO
3stoichiometric proportion take Bi
2o
3, MgO, TiO
2and Pb
3o
4material powder;
Two, the Bi accounting for raw material gross weight 30% is taken
2o
3and B
2o
3as flux, fully mix obtain crystal growth with rise expect;
Three, will rise to expect and load in platinum crucible and seal, the platinum crucible of good seal loads in skirt, and then is placed in crystal growing furnace;
Four, crucible is warming up to 900 DEG C through 6h, and be incubated 6h, then 1200 DEG C are warming up to through 8h, and be incubated 10h, raw material is all melted, then crucible declines with the speed of 1.0mm/h, the temperature gradient field in crystal growing furnace between high-temperature region and low-temperature space, and melt gradually crystalline growth becomes crystal; Grow complete, the speed of crucible 100 DEG C/h is cooled to room temperature, and crystal is come out of the stove;
Five, crystal growth completes, and crystal is come out of the stove, and carefully peels off crucible, takes out crystal;
Six, crystal boule acetic acid is soaked to remove flux Bi
2o
3and B
2o
3, then after deionized water washing, namely obtain titanium magnesium acid bismuth-lead titanates high-temperature piezoelectric monocrystalline;
The working temperature interval of the titanium magnesium acid bismuth-lead titanate high-temperature piezoelectric material prepared in the present embodiment is room temperature-565 DEG C, the dielectric constant 135F/m-160000F/m in working temperature interval.
Embodiment 11
One, by chemical formula 0.25Bi (Mg
1/2ti
1/2) O
3-0.75PbTiO
3+ 0.1mol%MnO
2stoichiometric proportion take Bi
2o
3, MgO, TiO
2, Pb
3o
4and MnO
2material powder;
Two, PbO, Bi of accounting for raw material gross weight 40% is taken
2o
3and B
2o
3as flux, fully mix obtain crystal growth with rise expect;
Three, will rise to expect and load in platinum crucible and seal, the platinum crucible of good seal loads in skirt, and then is placed in crystal growing furnace;
Four, crucible is warming up to 1000 DEG C through 8h, and be incubated 8h, then 1280 DEG C are warming up to through 4h, and be incubated 12h, raw material is all melted, then crucible declines with the speed of 1.2mm/h, the temperature gradient field in crystal growing furnace between high-temperature region and low-temperature space, and melt gradually crystalline growth becomes crystal; Grow complete, the speed of crucible 200 DEG C/h is cooled to room temperature, and crystal is come out of the stove;
Five, crystal growth completes, and crystal is come out of the stove, and carefully peels off crucible, takes out crystal;
Six, crystal boule acetic acid is soaked to remove flux PbO, Bi
2o
3and B
2o
3, after deionized water washing, then namely obtain the titanium magnesium acid bismuth-lead titanates high-temperature piezoelectric monocrystalline mixing manganese.
Embodiment 12
One, by chemical formula 0.40Bi (Mg
1/2ti
1/2) O
3-0.60PbTiO
3the stoichiometric proportion of-1mol%BaO takes Bi
2o
3, MgO, TiO
2, Pb
3o
4with BaO material powder;
Two, take account for raw material gross weight 50% NaCl and KCl as flux, fully mix obtain crystal growth with rise expect;
Three, will rise to expect and load in platinum crucible and seal, the platinum crucible of good seal is putting into alumina crucible, is then placed in Muffle furnace;
Four, in Muffle furnace, temperature from ambient is warming up to 1000 DEG C through 6h and is incubated 8h, then after 6h is warming up to 1300 DEG C, is incubated 4h, and in Muffle furnace, temperature is down to 1050 DEG C with the speed of 0.5 DEG C/h subsequently, then naturally cools to room temperature;
Five, crystal growth completes, and crystal is come out of the stove, and carefully peels off crucible, takes out crystal;
Six, crystal boule is soaked in water remove flux NaCl and KCl, after deionized water washing, then namely obtains the titanium magnesium acid bismuth-lead titanates high-temperature piezoelectric monocrystalline mixing barium.
Embodiment 13
One, by chemical formula 0.45Bi (Mg
1/2ti
1/2) O
3-0.55PbTiO
3-5mol%Nb
2o
5stoichiometric proportion take Bi
2o
3, MgO, TiO
2, Pb
3o
4and Nb
2o
5material powder;
Two, the PbF accounting for raw material gross weight 30% is taken
2, BiF
3and B
2o
3as flux, fully mix obtain crystal growth with rise expect;
Three, will rise to expect and load in platinum crucible and seal, the platinum crucible of good seal is putting into alumina crucible, is then placed in Muffle furnace;
Four, in Muffle furnace, temperature from ambient is warming up to 800 DEG C through 6h and is incubated 6h, then after 8h is warming up to 1300 DEG C, is incubated 10h, and in Muffle furnace, temperature is down to 950 DEG C with the speed of 2 DEG C/h subsequently, then naturally cools to room temperature;
Five, crystal growth completes, and crystal is come out of the stove, and carefully peels off crucible, takes out crystal;
Six, crystal boule acetic acid is soaked to remove flux PbF
2, BiF
3and B
2o
3, after deionized water washing, then namely obtain the titanium magnesium acid bismuth-lead titanates high-temperature piezoelectric monocrystalline mixing niobium.
Claims (10)
1. titanium magnesium acid bismuth-lead titanate high-temperature piezoelectric material, is characterized in that, described titanium magnesium acid bismuth-lead titanate high-temperature piezoelectric material has ABO
3perovskite composite oxide structure, the chemical formula of composition is (1-x) Bi (Mg
1/2ti
1/2) O
3-xPbTiO
3+ yA
2o
a+ zB
2o
b, wherein 0.50<x<1, elements A is ABO
3middle A position doped chemical, is selected from Li
+, Na
+, K
+, Ba
2+, Sr
2+, Ca
2+, and La
3+in at least one, element B is ABO
3middle B position doped chemical, is selected from Zn
2+, Ni
2+, Mn
2+, Sc
3+, Fe
3+, In
3+, Ga
3+, Co
3+, Cr
3+, Mn
3+, Mn
4+, Zr
4+, Nb
5+, Ta
5+, Sb
5+, V
5+, and W
6+in at least one, a is the doping valence state of elements A, and b is the doping valence state of element B, 0≤y≤5mol%, 0≤z≤10mol%, and y+z≤10mol%.
2. titanium magnesium acid bismuth-lead titanate high-temperature piezoelectric material according to claim 1, is characterized in that, 0.5 < x≤0.70.
3. titanium magnesium acid bismuth-lead titanate high-temperature piezoelectric material according to claim 1 and 2, it is characterized in that, the working temperature interval of described titanium magnesium acid bismuth-lead titanate high-temperature piezoelectric material is room temperature-600 DEG C, the dielectric constant 40F/m-180000F/m in working temperature interval.
4. the preparation method of arbitrary described titanium magnesium acid bismuth-lead titanate high-temperature piezoelectric material in claim 1-3, it is characterized in that, described method comprises:
1) according to the mol ratio in the chemical formula of described titanium magnesium acid bismuth-lead titanate high-temperature piezoelectric material between metallic element, take metal oxide powder as material powder, wherein, the oxide of Bi is Bi
2o
3, the oxide of Mg is the oxide of MgO, Ti is TiO
2, the oxide of Pb is PbO and/or Pb
3o
4;
2) flux into material powder quality 20-90% is taken, with material powder Homogeneous phase mixing, obtain preparing rising of described titanium magnesium acid bismuth-lead titanate high-temperature piezoelectric material to expect, wherein flux be lead oxide, lead orthoplumbate, lead fluoride, bismuth oxide, at least one of fluoridizing in bismuth, boron oxide, sodium chloride, potassium chloride;
3) by step 2) prepare rise expect, successively through isothermal holding and cooling process, obtain described titanium magnesium acid bismuth-lead titanate high-temperature piezoelectric material crystal boule, wherein, the parameter of isothermal holding is: 1100-1300 DEG C insulation 2-20 hour; Cooling is treated to, and is cooled to room temperature with the speed of 0.5-200 DEG C/h;
4) crystal boule step 3) prepared carries out pickling, obtains described titanium magnesium acid bismuth-lead titanate high-temperature piezoelectric material.
5. preparation method according to claim 4, is characterized in that, step 2) in, flux is material powder quality 20-60%.
6. the preparation method according to claim 4 or 5, it is characterized in that, in step 3), first described is expected in the platinum crucible be sealed in, be placed in again in alumina crucible and carry out the process that is incubated and lowers the temperature, wherein, described platinum crucible has 1 layer, 2 layers or 3 layers, and the thickness of every one deck is 0.1-0.2mm.
7., according to described preparation method arbitrary in claim 4-6, it is characterized in that, in step 3), isothermal holding is specially: after being first warming up to 700-1000 DEG C through 2-10 hours, insulation 2-20 hour, then be warming up to 1100-1300 DEG C through 2-5 hours, insulation 2-20 hour.
8. according to described preparation method arbitrary in claim 4-7, it is characterized in that, in step 3), described isothermal holding and cooling process are carried out in Muffle furnace, and cooling is treated to: be first cooled to 950-1050 DEG C with 0.5-100 DEG C/h, then be cooled to room temperature.
9. according to described preparation method arbitrary in claim 4-8, it is characterized in that, in step 3), described isothermal holding and cooling process are carried out in crystal growing furnace, cooling is treated to: by rising to expect and to decline with the speed of 0.1-1.2mm/ hour through second time isothermal holding, 1100-1300 DEG C of high-temperature region in crystal growing furnace and the length between 800-1000 DEG C of low-temperature space are the temperature gradient field of 50-100mm, then are cooled to room temperature.
10. according to described preparation method arbitrary in claim 4-9, it is characterized in that, in step 4), adopt acetic acid to carry out acidity.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410424420.2A CN105374931B (en) | 2014-08-26 | 2014-08-26 | Titanium magnesium acid bismuth-lead titanate high-temperature piezoelectric material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410424420.2A CN105374931B (en) | 2014-08-26 | 2014-08-26 | Titanium magnesium acid bismuth-lead titanate high-temperature piezoelectric material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105374931A true CN105374931A (en) | 2016-03-02 |
| CN105374931B CN105374931B (en) | 2018-05-08 |
Family
ID=55376919
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410424420.2A Active CN105374931B (en) | 2014-08-26 | 2014-08-26 | Titanium magnesium acid bismuth-lead titanate high-temperature piezoelectric material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105374931B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105624784A (en) * | 2014-10-28 | 2016-06-01 | 中国科学院上海硅酸盐研究所 | Tetragonal phase bismuth magnesium titanate-lead titanate base piezoelectric monocrystal suitable for high temperature field, and preparation method thereof |
| CN105624791A (en) * | 2014-10-28 | 2016-06-01 | 中国科学院上海硅酸盐研究所 | Preparation method of tetragonal phase bismuth magnesium titanate-lead titanate base piezoelectric monocrystals |
| CN107721410A (en) * | 2017-08-26 | 2018-02-23 | 华中科技大学 | A kind of preparation of binary high-temperature piezoelectric ceramics |
| CN108409319A (en) * | 2018-03-06 | 2018-08-17 | 同济大学 | The lead-free ceramics material and preparation method thereof of high energy storage density and charge-discharge performance |
| CN110723970A (en) * | 2019-11-13 | 2020-01-24 | 西安工业大学 | High-temperature electronic ceramic material with high temperature stability and preparation method thereof |
| CN111939895A (en) * | 2020-08-24 | 2020-11-17 | 浙江工业大学 | Bismuth oxide supported lead dioxide catalyst with different morphologies and preparation method and application thereof |
| CN116854472A (en) * | 2023-09-04 | 2023-10-10 | 中国科学院上海硅酸盐研究所 | Microwave dielectric material and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101857432A (en) * | 2010-06-11 | 2010-10-13 | 天津大学 | Magnesium titanate bismuth-lead titanate piezoelectric ceramics suitable for high-temperature field |
| CN102051685A (en) * | 2009-10-28 | 2011-05-11 | 中国科学院福建物质结构研究所 | Novel ferroelectric single-crystal lead ytterbium niobate-lead magnesium niobate-lead titanate |
| CN103774228A (en) * | 2014-02-26 | 2014-05-07 | 西安工业大学 | Lead scandium niobate-lead magnesium diniobate-lead titanate ferroelectric monocrystal and preparation method thereof |
-
2014
- 2014-08-26 CN CN201410424420.2A patent/CN105374931B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102051685A (en) * | 2009-10-28 | 2011-05-11 | 中国科学院福建物质结构研究所 | Novel ferroelectric single-crystal lead ytterbium niobate-lead magnesium niobate-lead titanate |
| CN101857432A (en) * | 2010-06-11 | 2010-10-13 | 天津大学 | Magnesium titanate bismuth-lead titanate piezoelectric ceramics suitable for high-temperature field |
| CN103774228A (en) * | 2014-02-26 | 2014-05-07 | 西安工业大学 | Lead scandium niobate-lead magnesium diniobate-lead titanate ferroelectric monocrystal and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| PENGHAO HU等: "Zero thermal expansion in (1 x)PbTiO3–xBi(Mg,Ti)1/2O3 piezoceramics", 《JOURNAL OF MATERIALS CHEMISTRY》 * |
| RUITING SUN等: "Dielectric and polar order behaviors of BaTiO3-Bi(Mg1/2Ti1/2)O3 ceramics", 《APPLIED PHYSICS A》 * |
| 赵丽艳: "高性能高温压电陶瓷的研究", 《长春理工大学硕士学位论文》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105624784A (en) * | 2014-10-28 | 2016-06-01 | 中国科学院上海硅酸盐研究所 | Tetragonal phase bismuth magnesium titanate-lead titanate base piezoelectric monocrystal suitable for high temperature field, and preparation method thereof |
| CN105624791A (en) * | 2014-10-28 | 2016-06-01 | 中国科学院上海硅酸盐研究所 | Preparation method of tetragonal phase bismuth magnesium titanate-lead titanate base piezoelectric monocrystals |
| CN105624784B (en) * | 2014-10-28 | 2018-04-03 | 中国科学院上海硅酸盐研究所 | Tetragonal titanium magnesium acid bismuth lead titanate piezoelectric monocrystal suitable for high-temperature field and preparation method thereof |
| 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 |
| CN107721410A (en) * | 2017-08-26 | 2018-02-23 | 华中科技大学 | A kind of preparation of binary high-temperature piezoelectric ceramics |
| CN108409319A (en) * | 2018-03-06 | 2018-08-17 | 同济大学 | The lead-free ceramics material and preparation method thereof of high energy storage density and charge-discharge performance |
| CN108409319B (en) * | 2018-03-06 | 2021-03-26 | 同济大学 | Lead-free ceramic material with high energy storage density and charge-discharge performance and preparation method thereof |
| CN110723970A (en) * | 2019-11-13 | 2020-01-24 | 西安工业大学 | High-temperature electronic ceramic material with high temperature stability and preparation method thereof |
| CN111939895A (en) * | 2020-08-24 | 2020-11-17 | 浙江工业大学 | Bismuth oxide supported lead dioxide catalyst with different morphologies and preparation method and application thereof |
| CN116854472A (en) * | 2023-09-04 | 2023-10-10 | 中国科学院上海硅酸盐研究所 | Microwave dielectric material and preparation method thereof |
| CN116854472B (en) * | 2023-09-04 | 2023-12-08 | 中国科学院上海硅酸盐研究所 | Microwave dielectric material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105374931B (en) | 2018-05-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105374931A (en) | Bi(Mg1/2Ti1/2)O3-PbTiO3(BMT-PT)-based high-temperature piezoelectric material and preparation method thereof | |
| CN101913868B (en) | Method for preparing potassium-sodium niobate textured ceramic and potassium-sodium niobate single crystal | |
| CN103771855B (en) | Sodium potassium niobate base leadless piezoelectric ceramics material | |
| CN103541014A (en) | Lead-free high-voltage active crystal material and preparation method thereof | |
| CN102584195B (en) | Bismuth-based perovskite type leadless piezoelectric ceramic and low-temperature preparation method thereof | |
| CN102817080A (en) | Lead lutetioniobate-lead magnesioniobate-lead titanate ternary-system relaxation ferroelectric monocrystal and preparation method thereof | |
| CN102557635A (en) | Sodium niobate lithium tantalate series lead-free piezoelectric ceramic composite | |
| CN111892400A (en) | High-transmittance high-entropy transparent ceramic and preparation method thereof | |
| Yamatoh et al. | Polymerizable complex synthesis of lead-free ferroelectric Na0. 5Bi0. 5TiO3 suppressing evaporation of sodium and bismuth | |
| CN104152999A (en) | Potassium-sodium niobate-based leadless piezoelectric monocrystalline and growth method therefor | |
| CN102766905B (en) | Erbium ion activated 1.55 micron waveband gallate laser crystalss and preparation method thereof | |
| CN103351858A (en) | Rare-earth-doped luminescent ferroelectric material and preparation method thereof | |
| CN102766906A (en) | Erbium ion activated 3-micron wave-band gallate laser crystal and its preparation method | |
| CN104372409A (en) | Ternary relaxor-based ferroelectric piezoelectric single crystal and growing method thereof | |
| CN102584194B (en) | Perovskite leadless piezoelectric ceramic used at high temperature and preparation method thereof | |
| CN107268084A (en) | Potassium-sodium niobate-zirconic acid bismuth sodium leadless piezoelectric monocrystalline and its growing method | |
| CN107098701A (en) | Potassium-sodium niobate lithium zirconic acid potassium sodium bismuth scandium acid bismuth ternary series lead-free piezoelectric ceramic | |
| CN104152997B (en) | Quaternary system relaxation type monocrystalline piezoelectric material and its growing method | |
| CN104131333B (en) | Method for preparing K0.5Na0.5NbO3 single crystal | |
| Politova et al. | Phase transitions, piezo-and ferroelectric properties of BiScO3-PbTiO3 solid solutions | |
| CN105624784B (en) | Tetragonal titanium magnesium acid bismuth lead titanate piezoelectric monocrystal suitable for high-temperature field and preparation method thereof | |
| GB2417243A (en) | Complex oxide having p-type thermoelectric characteristics | |
| CN102817068B (en) | A kind of preparation method of sodium bismuth titanate-lead titanate piezoelectric monocrystal | |
| CN103469307B (en) | The potassium-sodium niobate-based piezoquartz of Tetragonal lithium antimony tantalum codoped | |
| JPWO2012002509A1 (en) | Thermoelectric conversion material manufacturing method, thermoelectric conversion material, and manufacturing apparatus used in the manufacturing method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |