CN103979955B - Preparing method of barium titanate based leadless piezoceramic material doped and modified by lithium-aluminum ion pair - Google Patents
Preparing method of barium titanate based leadless piezoceramic material doped and modified by lithium-aluminum ion pair Download PDFInfo
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- CN103979955B CN103979955B CN201410200916.1A CN201410200916A CN103979955B CN 103979955 B CN103979955 B CN 103979955B CN 201410200916 A CN201410200916 A CN 201410200916A CN 103979955 B CN103979955 B CN 103979955B
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Abstract
The invention relates to a preparing method of a barium titanate based leadless piezoceramic material with high piezoelectric property, and particularly to a preparing method of a barium titanate based leadless piezoceramic material doped and modified by a lithium-aluminum ion pair. The objective of the invention is to overcome a problem that barium titanate based leadless piezoceramic materials prepared from common raw materials and by traditional solid phase synthesis methods are poor in piezoelectric property. The composition of the barium titanate based leadless ceramic provided by the invention is shown as Ba<1-x>(Li<0.5>Al<0.5>)xTi<1-x>Si<x>O3, wherein 0.02<=x<=0.08 mol. The barium titanate based leadless piezoceramic provided by the invention is prepared from common raw materials and by a traditional synthesis method. A system is a perovskite phase. When the x is 2-8 mol%, the Li<+>-Al<3+> ion pair exists in the ceramic, so that the piezoelectric constant d<33> is 300-400 pC/N and the electromechanical coupling factor kp is 0.35-0.45. The preparation process is simple and the cost is low.
Description
Technical field
The invention belongs to lead-free piezoceramic material field, be specifically related to the preparation method with high tension performance barium titanate based lead-free piezoceramic material.
Background technology
In recent years, due to leaded in Pb-based lanthanumdoped zirconate titanates (PZT) ceramic systems, preparation, use and waste treatment process in all easy in environment, thus just inexorable trend is become to the exploitation of leadless piezoelectric ceramics.Barium titanate (BaTiO
3, BT) and pottery is the Lead-free ferroelectric ceramics more Zao than PZT ceramic applications.Such as, the thin brilliant BT piezoelectric ceramics prepared by fine powder and special sintering method (two-step sintering, discharge plasma sintering, template grain growth), its piezoelectric constant d
33be optimized to 300-400pC/N.But the piezoelectric constant of the BT base pottery prepared by common raw material and conventional solid synthetic method is usually smaller, only has 200-300pC/N.
To having ABO
3the ferroelectric ceramic(s) (as PZT, BT, potassium-sodium niobate (KNN) etc.) of type perovskite structure, obtaining the most basic approach of large piezoelectric effect has two kinds: one to be the accurate homotype phase boundary (MPB) of design, as PZT system, as dividing close to Pb (Zr
0.52ti
0.48) O
3time, the phase transformation brought out by composition has excellent piezoelectric and dielectric properties by causing PZT base pottery near MPB; Two is utilize many types of phase in version (PPT), as KNN system, when orthorhombic phase is down near room temperature to the phase transition temperature of Tetragonal, utilizes the orthorhombic phase of temperature-driven also can produce large piezoelectric property (d to the phase transformation of Tetragonal
33=300-400pC/N).According in found Patents, yet there are no dopant ion to the preparation of barium titanate-based lead-free piezoelectric ceramics of modification and the research of piezoelectric property thereof.
Publication number be CN 102249671A (application number 201110126758.6) patent document discloses a kind of barium titanate based lead-free piezoceramic material and preparation method thereof, its bulk composition molecular formula is Ba
xca
ysr
1-x-y(Ti
wco
1-w) O
3, wherein 0.80≤x≤0.98,0.01≤y≤0.15,0.83≤w≤0.99, supplementary component comprises the Al accounting for bulk composition 0.08 ~ 0.25wt%
2o
3with the MgO of 0.02 ~ 0.20wt%, this material has two-step sintering method to prepare, its piezoelectric constant d
33reach 164pC/N, electromechanical coupling factor k
preach 0.348.Publication number is that patent document discloses of CN 101182203A (application number 200710114644.3) a kind ofly has the barium titanate based piezoelectric ceramic materials of average grain size 0.2-7.5 μm, its piezoelectric property d by solid-phase synthesis preparation
33value is greater than 225pC/N.Publication number is the barium phthalate base piezoelectric that patent document discloses a kind of modification of CN 101333106A (application number 200810138722.8), and its component is Ba (Ti
1-x[Zr
zsn
1-z]
x) O
3.yCuO, wherein x=0.001-0.10, y=0.001-0.07, z=0-1, this kind of material has that electromechanical coupling factor is large and mechanical quality factor is high and the stability good advantage of piezoelectric property.In patent disclosed in these, the piezoelectricity level of barium titanate base piezoelectric ceramic only has about 200pC/N, obtains d
33>300pC/N is very difficult thing.
Summary of the invention
The object of the invention is, in order to solve the poor problem of the barium titanate-based lead-free piezoelectric ceramics piezoelectric property that utilizes common raw material and conventional solid synthesis method to prepare, to provide the preparation method of lithium-aluminum ion to the barium titanate based lead-free piezoceramic material of doping vario-property.
Lithium-aluminum ion of the present invention is to the barium titanate based lead-free piezoceramic material of doping vario-property, and its chemical constitution general formula is Ba
1-x(Li
0.5al
0.5)
xti
1-xsi
xo
3; It is by BaCO
3, TiO
2, Li
2o, Al
2o
3and SiO
2stoichiometrically Ba
1-x(Li
0.5al
0.5)
xti
1-xsi
xo
3make, wherein, described x=2 ~ 8mol%.
Lithium-aluminum ion of the present invention, to the preparation method of the barium titanate based lead-free piezoceramic material of doping vario-property, is prepared according to following steps:
One, prepare burden:
By raw material BaCO
3, TiO
2, Li
2o, Al
2o
3and SiO
2, stoichiometrically Ba
1-x(Li
0.5al
0.5)
xti
1-xsi
xo
3weigh; Wherein, x=2 ~ 8mol%;
Two, ball milling:
Ball grinder ball milling put into by raw material step one weighed, and ball-milling medium is dehydrated alcohol and zirconium oxide balls, and wherein, ball milling condition is: ratio of grinding media to material is (2 ~ 5): 1, and rotating speed is 300 ~ 350r/min, and Ball-milling Time is 6 ~ 12h; After ball milling, ball milling gained slurry is incubated oven dry 10 ~ 12h at 80 DEG C;
Three, pre-burning:
Corundum ceramic crucible put into by powder after step 2 being dried, is warming up to 1150 ~ 1250 DEG C with the temperature rise rate of 5 DEG C/min, insulation 2 ~ 5h;
Four, secondary ball milling:
Powder after step 3 pre-burning is put into ball grinder again, and ball-milling medium is dehydrated alcohol and zirconium oxide balls, and wherein, ball milling condition is: rotating speed is 300 ~ 350r/min, and Ball-milling Time is 6 ~ 12h; After ball milling, ball milling gained slurry is incubated oven dry 10 ~ 12h at 80 DEG C;
Five, granulation
After step 4 being dried, powder grinds, sieves, and then interpolation 5wt.% polyvinyl alcohol fully grinds and carries out granulation;
Six, shaping
Powder after step 5 granulation is put into mould, makes disk at the pressure of 8 ~ 10MPa;
Seven, binder removal
The disk of step 6 is put into sintering oven, is warming up to 500 DEG C with the temperature rise rate of 1 DEG C/min, insulation 1h carries out binder removal;
Eight, sinter
Disk after binder removal in step 7 is put into corundum ceramic crucible, imbeds barium carbonate powder, be warming up to 1300 ~ 1400 DEG C with the temperature rise rate of 5 DEG C/min, insulation 2 ~ 5h, is chilled to room temperature with stove, obtains Ba
1-x(Li
0.5al
0.5)
xti
1-xsi
xo
3leadless piezoelectric ceramics;
Nine, plated electrode
By the Ba obtained in step 8
1-x(Li
0.5al
0.5)
xti
1-xsi
xo
3leadless piezoelectric ceramics surface finish, adopt the method for magnetron sputtering, ceramic plate upper and lower surface after a polish sputters one deck silver electrode; Then the leadless piezoelectric ceramics with electrode is put into sintering oven to anneal under temperature is 500 DEG C of conditions, insulation 30min;
Ten, polarize
Leadless piezoelectric ceramics after step 8 being sintered is the 30min that polarizes in the silicone oil of 80 DEG C as temperature, and wherein, polarized electric field 1 ~ 3kV/mm, namely completes.
Lithium-aluminum ion of the present invention is to the barium titanate based lead-free piezoceramic material of doping vario-property, and its chemical constitution general formula is xLAS/BT; It is by BaTiO
3and LiAlSiO
4stoichiometrically xLAS/BT makes, wherein, and described x=2 ~ 8mol%.
Lithium-aluminum ion of the present invention, to the preparation method of the barium titanate based lead-free piezoceramic material of doping vario-property, is prepared according to following steps:
One, prepare burden
By raw material BaTiO
3and LiAlSiO
4stoichiometrically xLAS/BT weighs, wherein, and x=2 ~ 8mol%;
Two, ball milling
Ball grinder ball milling put into by raw material step one weighed, and ball-milling medium is dehydrated alcohol and zirconium oxide balls, and wherein, ball milling condition is: ratio of grinding media to material is (5 ~ 10): 1, and rotating speed is 300 ~ 350r/min, and Ball-milling Time is 6 ~ 12h; After ball milling, ball milling gained slurry is incubated oven dry 10 ~ 12h under temperature is 80 DEG C of conditions, then grinds, sieve, obtain powder;
Three, granulation
After step 2 being dried, powder grinds, sieves, and the polyvinyl alcohol then adding 5wt.% fully grinds and carries out granulation;
Four, shaping
Powder after step 3 granulation is put into mould, makes disk at the pressure of 8 ~ 10MPa;
Five, binder removal
The disk of step 4 is put into sintering oven, is warming up to 500 DEG C with the temperature rise rate of 1 DEG C/min, insulation 1h carries out binder removal;
Six, sinter
Disk after binder removal in step 5 is put into corundum ceramic crucible, imbeds barium carbonate powder, be warming up to 1300 ~ 1400 DEG C with the temperature rise rate of 5 DEG C/min, insulation 2 ~ 5h, is chilled to room temperature with stove, obtains xLAS/BT lead-free piezoceramic material;
Seven, plated electrode
By the xLAS/BT lead-free piezoceramic material surface finish obtained in step 6, adopt the method for magnetron sputtering, the surface after leadless piezoelectric ceramics polishing sputters one deck silver electrode; Then the leadless piezoelectric ceramics with electrode is put into sintering oven to anneal under temperature is 500 DEG C of conditions, insulation 30min;
Eight, polarize
Pottery after step 7 plated electrode being placed in temperature is that the silicone oil of 80 DEG C polarizes, and wherein, polarized electric field is 1 ~ 3kV/mm, and the polarization time is 30min, namely completes.
Lithium-aluminum ion of the present invention is to the barium titanate based lead-free piezoceramic material of doping vario-property, and it is by BaCO
3and TiO
2ba/Ti=1:1 makes in molar ratio.
Lithium-aluminum ion of the present invention, to the preparation method of the barium titanate based lead-free piezoceramic material of doping vario-property, is prepared according to following steps:
One, prepare burden
By raw material BaCO
3and TiO
2ba/Ti=1:1 weighs in molar ratio;
Two, ball milling
Load weighted for step one raw material is put into ball grinder ball milling, ball-milling medium is dehydrated alcohol and zirconium oxide balls, wherein, ball milling condition is: ratio of grinding media to material is (2 ~ 5): 1, rotating speed is 300 ~ 350r/min, Ball-milling Time is 12 ~ 24h, and ball milling gained slurry is incubated oven dry 10 ~ 12h at 80 DEG C;
Three, pre-burning
Powder after step 2 being sieved, as in crucible, is warming up to 1150 ~ 1250 DEG C with the temperature rise rate of 5 DEG C/min, and insulation 2 ~ 5h, then furnace cooling, obtain barium carbonate powder;
Four, secondary ball milling
By the barium carbonate powder obtained after step 3 pre-burning and eucryptite powder stoichiometrically xLAS/BT take, wherein, x=2 ~ 8mol%, then the barium carbonate powder taken and eucryptite powder are put into ball grinder ball milling, wherein, ball milling condition is: ball-milling medium is dehydrated alcohol and zirconium oxide balls, ratio of grinding media to material is (5 ~ 10): 1, rotating speed is 300 ~ 350r/min, and Ball-milling Time is 6 ~ 10h, and ball milling gained slurry is incubated oven dry 10 ~ 12h at 80 DEG C;
Five, granulation
After step 4 being dried, powder grinds, sieves, and the polyvinyl alcohol then adding 5wt.% fully grinds and carries out granulation;
Six, shaping
Powder after step 5 granulation is put into mould, makes disk at the pressure of 8 ~ 10MPa;
Seven, binder removal
The disk of step 6 is put into sintering oven, is warming up to 500 DEG C with the temperature rise rate of 1 DEG C/min, insulation 1h carries out abundant binder removal;
Eight, sinter
Disk after binder removal in step 7 is put into corundum ceramic crucible, imbeds barium carbonate powder, be warming up to 1300 ~ 1400 DEG C with the temperature rise rate of 5 DEG C/min, insulation 2 ~ 5h, is chilled to room temperature with stove, obtains xLAS/BT leadless piezoelectric ceramics;
Nine, plated electrode
By the xLAS/BT leadless piezoelectric ceramics surface finish sintered in step 8, adopt the method for magnetron sputtering, the surface that pottery is bright and clean sputters one deck silver electrode; Then the ceramics sample with electrode is put into sintering oven 500 DEG C annealing, insulation 30min;
Ten, polarize
By the ceramics sample of step 9 as in the silicone oil of 80 DEG C, the polarization time is 30min, and polarized electric field is 1 ~ 3kV/mm, namely completes.
The present invention comprises following beneficial effect:
Lithium-aluminum ion that the present invention provides is to (Li
+-Al
3+) the barium titanate based piezoelectric ceramic materials d of doping vario-property
33the piezoelectric property of 300-400pC/N is brought up to by the level of common 200pC/N.
The invention provides a kind of lithium-aluminum ion to (Li
+-Al
3+) barium titanate based piezoelectric ceramic materials of doping vario-property, this body of material component molecules formula is Ba
1-x(Li
0.5al
0.5)
xti
1-xsi
xo
3, wherein 0.02≤x≤0.08mol.Prepare this material desired raw material to be easy to get, with low cost, preparation technology is simple, and prepared barium titanate base piezoelectric ceramic has excellent piezoelectric property.
The present invention utilizes solid-phase synthesis to prepare lithium-aluminum ion to (Li
+-Al
3+) the barium titanate-based lead-free piezoelectric ceramics of doping vario-property, by the doping vario-property that lithium-aluminum ion is right, the piezoelectric property of barium titanate base piezoelectric ceramic is greatly improved.Up to the present yet there are no the report utilizing ion pair doping vario-property to improve barium titanate-based lead-free piezoelectric ceramics piezoelectric property aspect.
Accompanying drawing illustrates:
Fig. 1 to execute under example 1 operational condition gained lithium-aluminum ion to (Li
+-Al
3+) XRD figure of barium titanate ceramics of doping vario-property;
Fig. 2 be to execute under example 1 operational condition lithium-aluminum ion to doping after, the lattice parameter of barium titanate and tetragonality are with the variation relation figure of LAS content; Wherein,
for the variation relation of lattice parameter a,
for the variation relation of lattice parameter c,
for the variation relation of tetragonality (c/a);
Fig. 3 is that lithium-aluminum ion is on the schematic diagram of doping on the impact of barium titanate lattice;
Fig. 4 is executing the SEM figure of gained high piezoelectric constant barium titanate ceramics under example 1 operational condition;
Fig. 5 is at the piezoelectric constant (d executing gained barium titanate base piezoelectric ceramic under example 1 operational condition
33) and against piezo-electric modulus (dS/dE) and pure barium titanate piezoelectric ceramics Performance comparision; Wherein,
for piezoelectric constant (d
33) graphic representation;
for the graphic representation of inverse piezo-electric modulus (dS/dE);
Fig. 6 is at the electromechanical coupling factor executing gained barium titanate ceramics under example 1 operational condition.
Embodiment:
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Specifically embodiment one: the lithium-aluminum ion of present embodiment is to the barium titanate based lead-free piezoceramic material of doping vario-property, and its chemical constitution general formula is Ba
1-x(Li
0.5al
0.5)
xti
1-xsi
xo
3; It is by BaCO
3, TiO
2, Li
2o, Al
2o
3and SiO
2stoichiometrically Ba
1-x(Li
0.5al
0.5)
xti
1-xsi
xo
3make, wherein, described x=2 ~ 8mol%.
Embodiment two: present embodiment and specifically embodiment one are unlike described x=4 ~ 6mol%.Other is identical with embodiment one.
Lithium-aluminum ion that present embodiment provides is to (Li
+-Al
3+) the barium titanate based piezoelectric ceramic materials d of doping vario-property
33the piezoelectric property of 300-400pC/N is brought up to by the level of common 200pC/N.
Present embodiment provides a kind of lithium-aluminum ion to (Li
+-Al
3+) barium titanate based piezoelectric ceramic materials of doping vario-property, this body of material component molecules formula is Ba
1-x(Li
0.5al
0.5)
xti
1-xsi
xo
3, wherein 0.02≤x≤0.08mol.Up to the present yet there are no the report utilizing ion pair doping vario-property to improve barium titanate-based lead-free piezoelectric ceramics piezoelectric property aspect.
Embodiment three: the lithium-aluminum ion of present embodiment, to the preparation method of the barium titanate based lead-free piezoceramic material of doping vario-property, is prepared according to following steps:
One, prepare burden:
By raw material BaCO
3, TiO
2, Li
2o, Al
2o
3and SiO
2, stoichiometrically Ba
1-x(Li
0.5al
0.5)
xti
1-xsi
xo
3weigh; Wherein, x=2 ~ 8mol%;
Two, ball milling:
Ball grinder ball milling put into by raw material step one weighed, and ball-milling medium is dehydrated alcohol and zirconium oxide balls, and wherein, ball milling condition is: ratio of grinding media to material is (2 ~ 5): 1, and rotating speed is 300 ~ 350r/min, and Ball-milling Time is 6 ~ 12h; After ball milling, ball milling gained slurry is incubated oven dry 10 ~ 12h at 80 DEG C;
Three, pre-burning:
Corundum ceramic crucible put into by powder after step 2 being dried, is warming up to 1150 ~ 1250 DEG C with the temperature rise rate of 5 DEG C/min, insulation 2 ~ 5h;
Four, secondary ball milling:
Powder after step 3 pre-burning is put into ball grinder again, and ball-milling medium is dehydrated alcohol and zirconium oxide balls, and wherein, ball milling condition is: rotating speed is 300 ~ 350r/min, and Ball-milling Time is 6 ~ 12h; After ball milling, ball milling gained slurry is incubated oven dry 10 ~ 12h at 80 DEG C;
Five, granulation
After step 4 being dried, powder grinds, sieves, and then interpolation 5wt.% polyvinyl alcohol fully grinds and carries out granulation;
Six, shaping
Powder after step 5 granulation is put into mould, makes disk at the pressure of 8 ~ 10MPa;
Seven, binder removal
The disk of step 6 is put into sintering oven, is warming up to 500 DEG C with the temperature rise rate of 1 DEG C/min, insulation 1h carries out binder removal;
Eight, sinter
Disk after binder removal in step 7 is put into corundum ceramic crucible, imbeds barium carbonate powder, be warming up to 1300 ~ 1400 DEG C with the temperature rise rate of 5 DEG C/min, insulation 2 ~ 5h, is chilled to room temperature with stove, obtains Ba
1-x(Li
0.5al
0.5)
xti
1-xsi
xo
3leadless piezoelectric ceramics;
Nine, plated electrode
By the Ba obtained in step 8
1-x(Li
0.5al
0.5)
xti
1-xsi
xo
3leadless piezoelectric ceramics surface finish, adopt the method for magnetron sputtering, ceramic plate upper and lower surface after a polish sputters one deck silver electrode; Then the leadless piezoelectric ceramics with electrode is put into sintering oven to anneal under temperature is 500 DEG C of conditions, insulation 30min;
Ten, polarize
Leadless piezoelectric ceramics after step 8 being sintered is the 30min that polarizes in the silicone oil of 80 DEG C as temperature, and wherein, polarized electric field 1 ~ 3kV/mm, namely completes.
Lithium-aluminum ion that present embodiment provides is to (Li
+-Al
3+) the barium titanate based piezoelectric ceramic materials d of doping vario-property
33the piezoelectric property of 300-400pC/N is brought up to by the level of common 200pC/N.
Present embodiment provides a kind of lithium-aluminum ion to (Li
+-Al
3+) barium titanate based piezoelectric ceramic materials of doping vario-property, this body of material component molecules formula is Ba
1-x(Li
0.5al
0.5)
xti
1-xsi
xo
3, wherein 0.02≤x≤0.08mol.Prepare this material desired raw material to be easy to get, with low cost, preparation technology is simple, and prepared barium titanate base piezoelectric ceramic has excellent piezoelectric property.
Present embodiment utilizes solid-phase synthesis to prepare lithium-aluminum ion to (Li
+-Al
3+) the barium titanate-based lead-free piezoelectric ceramics of doping vario-property, by the doping vario-property that lithium-aluminum ion is right, the piezoelectric property of barium titanate base piezoelectric ceramic is greatly improved.Up to the present yet there are no the report utilizing ion pair doping vario-property to improve barium titanate-based lead-free piezoelectric ceramics piezoelectric property aspect.
Embodiment four: present embodiment and specifically embodiment three are unlike the x=4 ~ 6mol% described in step one.Other is identical with embodiment three.
Embodiment five: present embodiment and specifically embodiment three or four are unlike the x=5mol% described in step one.Other is identical with embodiment three or four.
Embodiment six: present embodiment and specifically one of embodiment three to five unlike: the ball milling condition described in step 2 is: ratio of grinding media to material is (3 ~ 5): 1, and rotating speed is 320 ~ 350r/min, and Ball-milling Time is 8 ~ 12h; After ball milling, ball milling gained slurry is incubated oven dry 10 ~ 12h at 80 DEG C.Other is identical with one of embodiment three to five.
Embodiment seven: present embodiment and specifically one of embodiment three to six unlike: be warming up to 1200 ~ 1250 DEG C with the temperature rise rate of 5 DEG C/min, insulation 3 ~ 5h described in step 3.Other is identical with one of embodiment three to six.
Embodiment eight: present embodiment and specifically one of embodiment three to seven unlike: be warming up to 1350 ~ 1400 DEG C with the temperature rise rate of 5 DEG C/min, insulation 3 ~ 5h described in step 8.Other is identical with one of embodiment three to seven.
Embodiment nine: present embodiment and specifically one of embodiment three to eight are unlike the polarized electric field 2kV/mm described in step 10.Other is identical with one of embodiment three to eight.
Embodiment ten: the lithium-aluminum ion of present embodiment is to the barium titanate based lead-free piezoceramic material of doping vario-property, and its chemical constitution general formula is xLAS/BT; It is by BaTiO
3and LiAlSiO
4stoichiometrically xLAS/BT makes, wherein, and described x=2 ~ 8mol%.
Present embodiment provides a kind of lithium-aluminum ion to (Li
+-Al
3+) barium titanate based piezoelectric ceramic materials of doping vario-property, this body of material component molecules formula is Ba
1-x(Li
0.5al
0.5)
xti
1-xsi
xo
3, wherein 0.02≤x≤0.08mol.Up to the present yet there are no the report utilizing ion pair doping vario-property to improve barium titanate-based lead-free piezoelectric ceramics piezoelectric property aspect.
Embodiment 11: present embodiment and specifically embodiment ten are unlike the x=4 ~ 6mol% described in step one.Other is identical with embodiment ten.
Embodiment 12: the lithium-aluminum ion of present embodiment, to the preparation method of the barium titanate based lead-free piezoceramic material of doping vario-property, is prepared according to following steps:
One, prepare burden
By raw material BaTiO
3and LiAlSiO
4stoichiometrically xLAS/BT weighs, wherein, and x=2 ~ 8mol%;
Two, ball milling
Ball grinder ball milling put into by raw material step one weighed, and ball-milling medium is dehydrated alcohol and zirconium oxide balls, and wherein, ball milling condition is: ratio of grinding media to material is (5 ~ 10): 1, and rotating speed is 300 ~ 350r/min, and Ball-milling Time is 6 ~ 12h; After ball milling, ball milling gained slurry is incubated oven dry 10 ~ 12h under temperature is 80 DEG C of conditions, then grinds, sieve, obtain powder;
Three, granulation
After step 2 being dried, powder grinds, sieves, and the polyvinyl alcohol then adding 5wt.% fully grinds and carries out granulation;
Four, shaping
Powder after step 3 granulation is put into mould, makes disk at the pressure of 8 ~ 10MPa;
Five, binder removal
The disk of step 4 is put into sintering oven, is warming up to 500 DEG C with the temperature rise rate of 1 DEG C/min, insulation 1h carries out binder removal;
Six, sinter
Disk after binder removal in step 5 is put into corundum ceramic crucible, imbeds barium carbonate powder, be warming up to 1300 ~ 1400 DEG C with the temperature rise rate of 5 DEG C/min, insulation 2 ~ 5h, is chilled to room temperature with stove, obtains xLAS/BT lead-free piezoceramic material;
Seven, plated electrode
By the xLAS/BT lead-free piezoceramic material surface finish obtained in step 6, adopt the method for magnetron sputtering, the surface after leadless piezoelectric ceramics polishing sputters one deck silver electrode; Then the leadless piezoelectric ceramics with electrode is put into sintering oven to anneal under temperature is 500 DEG C of conditions, insulation 30min;
Eight, polarize
Pottery after step 7 plated electrode being placed in temperature is that the silicone oil of 80 DEG C polarizes, and wherein, polarized electric field is 1 ~ 3kV/mm, and the polarization time is 30min, namely completes.
Lithium-aluminum ion that present embodiment provides is to (Li
+-Al
3+) the barium titanate based piezoelectric ceramic materials d of doping vario-property
33the piezoelectric property of 300-400pC/N is brought up to by the level of common 200pC/N.
Present embodiment provides a kind of lithium-aluminum ion to (Li
+-Al
3+) barium titanate based piezoelectric ceramic materials of doping vario-property, this body of material component molecules formula is Ba
1-x(Li
0.5al
0.5)
xti
1-xsi
xo
3, wherein 0.02≤x≤0.08mol.Prepare this material desired raw material to be easy to get, with low cost, preparation technology is simple, and prepared barium titanate base piezoelectric ceramic has excellent piezoelectric property.
Present embodiment utilizes solid-phase synthesis to prepare lithium-aluminum ion to (Li
+-Al
3+) the barium titanate-based lead-free piezoelectric ceramics of doping vario-property, by the doping vario-property that lithium-aluminum ion is right, the piezoelectric property of barium titanate base piezoelectric ceramic is greatly improved.Up to the present yet there are no the report utilizing ion pair doping vario-property to improve barium titanate-based lead-free piezoelectric ceramics piezoelectric property aspect.
Embodiment 13: present embodiment and specifically embodiment 12 are unlike the x=4 ~ 6mol% described in step one.Other is identical with embodiment 12.
Embodiment 14: present embodiment and specifically embodiment 12 or 13 are unlike the x=5mol% described in step one.Other is identical with embodiment 12 or 13.
Embodiment 15: present embodiment and specifically one of embodiment ten two to ten four unlike: the ball milling condition described in step 2 is: ratio of grinding media to material is (3 ~ 5): 1, and rotating speed is 320 ~ 350r/min, and Ball-milling Time is 8 ~ 12h; After ball milling, ball milling gained slurry is incubated oven dry 10 ~ 12h at 80 DEG C.Other is identical with one of embodiment ten two to ten four.
Embodiment 16: present embodiment and specifically one of embodiment ten two to ten five unlike: be warming up to 1350 ~ 1400 DEG C with the temperature rise rate of 5 DEG C/min, insulation 3 ~ 5h described in step 6.Other is identical with one of embodiment ten two to ten five.
Embodiment 17: present embodiment and specifically one of embodiment ten two to ten six are unlike the polarized electric field 2kV/mm described in step 8.Other is identical with one of embodiment ten two to ten six.
Embodiment 18: the lithium-aluminum ion of present embodiment is to the barium titanate based lead-free piezoceramic material of doping vario-property, and it is by BaCO
3and TiO
2ba/Ti=1:1 makes in molar ratio.
Present embodiment provides a kind of lithium-aluminum ion to (Li
+-Al
3+) barium titanate based piezoelectric ceramic materials of doping vario-property, this body of material component molecules formula is Ba
1-x(Li
0.5al
0.5)
xti
1-xsi
xo
3, wherein 0.02≤x≤0.08mol.Up to the present yet there are no the report utilizing ion pair doping vario-property to improve barium titanate-based lead-free piezoelectric ceramics piezoelectric property aspect.
Embodiment 19: the lithium-aluminum ion of present embodiment, to the preparation method of the barium titanate based lead-free piezoceramic material of doping vario-property, is prepared according to following steps:
One, prepare burden
By raw material BaCO
3and TiO
2ba/Ti=1:1 weighs in molar ratio;
Two, ball milling
Load weighted for step one raw material is put into ball grinder ball milling, ball-milling medium is dehydrated alcohol and zirconium oxide balls, wherein, ball milling condition is: ratio of grinding media to material is (2 ~ 5): 1, rotating speed is 300 ~ 350r/min, Ball-milling Time is 12 ~ 24h, and ball milling gained slurry is incubated oven dry 10 ~ 12h at 80 DEG C;
Three, pre-burning
Powder after step 2 being sieved, as in crucible, is warming up to 1150 ~ 1250 DEG C with the temperature rise rate of 5 DEG C/min, and insulation 2 ~ 5h, then furnace cooling, obtain barium carbonate powder;
Four, secondary ball milling
By the barium carbonate powder obtained after step 3 pre-burning and eucryptite powder stoichiometrically xLAS/BT take, wherein, x=2 ~ 8mol%, then the barium carbonate powder taken and eucryptite powder are put into ball grinder ball milling, wherein, ball milling condition is: ball-milling medium is dehydrated alcohol and zirconium oxide balls, ratio of grinding media to material is (5 ~ 10): 1, rotating speed is 300 ~ 350r/min, and Ball-milling Time is 6 ~ 10h, and ball milling gained slurry is incubated oven dry 10 ~ 12h at 80 DEG C;
Five, granulation
After step 4 being dried, powder grinds, sieves, and the polyvinyl alcohol then adding 5wt.% fully grinds and carries out granulation;
Six, shaping
Powder after step 5 granulation is put into mould, makes disk at the pressure of 8 ~ 10MPa;
Seven, binder removal
The disk of step 6 is put into sintering oven, is warming up to 500 DEG C with the temperature rise rate of 1 DEG C/min, insulation 1h carries out abundant binder removal;
Eight, sinter
Disk after binder removal in step 7 is put into corundum ceramic crucible, imbeds barium carbonate powder, be warming up to 1300 ~ 1400 DEG C with the temperature rise rate of 5 DEG C/min, insulation 2 ~ 5h, is chilled to room temperature with stove, obtains xLAS/BT leadless piezoelectric ceramics;
Nine, plated electrode
By the xLAS/BT leadless piezoelectric ceramics surface finish sintered in step 8, adopt the method for magnetron sputtering, the surface that pottery is bright and clean sputters one deck silver electrode; Then the ceramics sample with electrode is put into sintering oven 500 DEG C annealing, insulation 30min;
Ten, polarize
By the ceramics sample of step 9 as in the silicone oil of 80 DEG C, the polarization time is 30min, and polarized electric field is 1 ~ 3kV/mm, namely completes.
Lithium-aluminum ion that present embodiment provides is to (Li
+-Al
3+) the barium titanate based piezoelectric ceramic materials d of doping vario-property
33the piezoelectric property of 300-400pC/N is brought up to by the level of common 200pC/N.
Present embodiment provides a kind of lithium-aluminum ion to (Li
+-Al
3+) barium titanate based piezoelectric ceramic materials of doping vario-property, this body of material component molecules formula is Ba
1-x(Li
0.5al
0.5)
xti
1-xsi
xo
3, wherein 0.02≤x≤0.08mol.Prepare this material desired raw material to be easy to get, with low cost, preparation technology is simple, and prepared barium titanate base piezoelectric ceramic has excellent piezoelectric property.
Present embodiment utilizes solid-phase synthesis to prepare lithium-aluminum ion to (Li
+-Al
3+) the barium titanate-based lead-free piezoelectric ceramics of doping vario-property, by the doping vario-property that lithium-aluminum ion is right, the piezoelectric property of barium titanate base piezoelectric ceramic is greatly improved.Up to the present yet there are no the report utilizing ion pair doping vario-property to improve barium titanate-based lead-free piezoelectric ceramics piezoelectric property aspect.
Embodiment 20: present embodiment and specifically embodiment 19 unlike: the ball milling condition described in step 2 and four is: ratio of grinding media to material is (3 ~ 5): 1, and rotating speed is 320 ~ 350r/min, and Ball-milling Time is 8 ~ 12h; After ball milling, ball milling gained slurry is incubated oven dry 10 ~ 12h at 80 DEG C.Other is identical with embodiment 19.
Embodiment 21: present embodiment and specifically embodiment 19 or 20 unlike: be warming up to 1200 ~ 1250 DEG C with the temperature rise rate of 5 DEG C/min, insulation 3 ~ 5h described in step 3.Other is identical with embodiment 19 or 20.
Embodiment 22: one of present embodiment and specifically embodiment ten nine to two 11 unlike: be warming up to 1350 ~ 1400 DEG C with the temperature rise rate of 5 DEG C/min, insulation 3 ~ 5h described in step 8.Other is one of ten nine to two ten one identical with embodiment.
Embodiment 23: one of present embodiment and specifically embodiment ten nine to two 12 is unlike the polarized electric field 2kV/mm described in step 10.Other is one of ten nine to two ten two identical with embodiment.
Beneficial effect of the present invention is verified by following examples:
Embodiment 1
The preparation of the barium titanate based lead-free piezoceramic material of the ion pair doping vario-property of the present embodiment, carry out according to following steps:
(1) prepare burden
By raw material barium titanate (BaTiO
3, BT), eucryptite (LiAlSiO
4, LAS) stoichiometrically xLAS/BT (x=7.5mol%) weigh;
(2) ball milling
Step (1) load weighted raw material is put into ball grinder, and ball-milling medium is dehydrated alcohol and zirconium oxide balls, and ratio of grinding media to material is 5:1, and rotating speed is 300r/min, and ball milling is 6h, and ball milling gained slurry is incubated at 80 DEG C dries 12h;
(3) granulation
After step (2) being dried, powder grinds, sieves, and the PVA adding 5wt.% fully grinds and carries out granulation;
(4) shaping
Powder after step (3) granulation is put into stainless steel mould, makes at the pressure of 10MPa the disk that diameter is 10mm;
(5) binder removal
The disk of step (4) is put into sintering oven, is warming up to 500 DEG C with the temperature rise rate of 1 DEG C/min, insulation 1h carries out abundant binder removal;
(6) sinter
Disk after binder removal in step (5) is put into corundum ceramic crucible, imbed barium carbonate powder, and cover with crucible cover, 1350 DEG C are warming up to the temperature rise rate of 5 DEG C/min, insulation 2h, be chilled to room temperature with stove, obtain xLAS/BT (x=7.5mol%) leadless piezoelectric ceramics;
(6) plated electrode
By the ceramics sample surface finish sintered in step (5), thickness of sample is milled to about 1mm, adopts the method for magnetron sputtering, the surface that pottery is bright and clean sputters one deck silver electrode, then the ceramics sample with electrode is put into sintering oven 500 DEG C annealing, insulation 30min;
(7) polarize
By the ceramics sample of step (6) as the 30min that polarizes in the silicone oil of 80 DEG C, wherein, polarized electric field 3kV/mm, obtains barium titanate-based lead-free piezoelectric ceramics.
Fig. 1 gives under the condition of the present embodiment, and namely barium titanate base piezoelectric ceramic sinters the XRD figure of 2h at 1350 DEG C, and all ceramics samples are cubic Perovskite Phase as seen from Figure 1.According to mixing eucryptite (LiAlSiO
4) middle Li
+, Al
3+and Si
4+the valency of ion, we think Li
+and Al
3+the A position that ion doping enters in BT replaces Ba
2+, like this, the average valence of A position is 2+, can maintain the local electroneutrality in BT lattice.And in order to reduce electrostatic energy, Li
+and Al
3+ion will form lithium-aluminum ion pair as far as possible in same unit cell.Meanwhile, Si
4+the B position that ion doping enters in BT replaces Ti
4+.In addition, because Li
+and Al
3+average ionic radius compares Ba
2+little, Si
4+ionic radius is also than Ti
4+little, the doping of eucryptite is bound to cause the local distortion of BT lattice, as shown in Figure 3.
Lithium-aluminum ion on doping on barium titanate lattice parameter (a, c) and tetragonality (c/a) impact as shown in Figure 2, along with the increase of eucryptite (LAS) content, the lattice parameter c of barium titanate significantly decreases, and lattice parameter a decline is not obvious, it is very fast that result causes its tetragonality (c/a) to decline.
Fig. 4 gives under the condition of the present embodiment, and the SEM figure of barium titanate base piezoelectric ceramic, it is dense that visible ceramics sample sinters, no significant defect.
Fig. 5 gives under the condition of the present embodiment, the piezoelectric constant of barium titanate base piezoelectric ceramic and inverse piezo-electric modulus, visible, as x=7.5mol%, and the piezoelectric constant d of ceramics sample
33value is about 378pC/N, and inverse piezoelectric coefficient d S/dE is 540pm/V.
Fig. 6 gives the electromechanical coupling factor k of gained barium titanate base piezoelectric ceramic under the condition of the present embodiment
p, with pure barium titanate ceramic phase ratio, had significant improvement by the piezoelectric property of lithium-aluminum ion to the barium titanate based lead-free piezoceramic material of doping vario-property.
Embodiment 2
The preparation of the barium titanate based lead-free piezoceramic material of the ion pair doping vario-property of the present embodiment, carry out according to following steps:
(1) prepare burden
By raw material barium titanate (BaTiO
3), eucryptite (LiAlSiO
4) stoichiometrically xLAS/BT (x=4mol%) prepare;
(2) ball milling
Step (1) load weighted raw material is put into ball grinder, and ball-milling medium is dehydrated alcohol and zirconium oxide balls, and ratio of grinding media to material is 10:1, rotating speed 350r/min, ball milling 8h, and ball milling gained slurry is incubated at 80 DEG C dries 10h;
(3) granulation
After step (2) being dried, powder grinds, sieves, and the PVA adding 5wt.% fully grinds and carries out granulation;
(4) shaping
Powder after step (3) granulation is put into stainless steel mould, makes at the pressure of 10MPa the disk that diameter is 10mm;
(5) binder removal
The disk of step (4) is put into sintering oven, is warming up to 500 DEG C with the temperature rise rate of 1 DEG C/min, insulation 1h carries out abundant binder removal;
(6) sinter
Disk after binder removal in step (5) is put into corundum ceramic crucible, imbeds barium carbonate powder, and cover with crucible cover, 1400 DEG C are warming up to the temperature rise rate of 5 DEG C/min, insulation 2h, is chilled to room temperature with stove, obtains xLAS/BT (x=4mol%) leadless piezoelectric ceramics;
(6) plated electrode
By the ceramics sample surface finish sintered in step (5), thickness of sample is milled to about 1mm, adopts the method for magnetron sputtering, the surface that pottery is bright and clean sputters one deck silver electrode, then the ceramics sample with electrode is put into sintering oven 500 DEG C annealing, insulation 30min;
(7) polarize
By the ceramics sample of step (6) as the 30min that polarizes in the silicone oil of 80 DEG C, wherein, polarized electric field 2kV/mm, obtains barium titanate-based lead-free piezoelectric ceramics.
The barium titanate-based lead-free piezoelectric ceramics that the present embodiment obtains has piezoelectric constant d
33value is about 320pC/N.
Embodiment 3:
The preparation of the barium titanate based lead-free piezoceramic material of the ion pair doping vario-property of the present embodiment, carry out according to following steps:
(1) prepare burden
By raw material barium titanate (BaTiO
3), eucryptite (LiAlSiO
4) stoichiometrically xLAS/BT (x=7mol%) prepare;
(2) ball milling
Step (1) load weighted raw material is put into ball grinder, and ball-milling medium is dehydrated alcohol and zirconium oxide balls, and ratio of grinding media to material is 5:1, rotating speed 300r/min, ball milling 6h, and ball milling gained slurry is incubated at 80 DEG C dries 10h;
(3) granulation
After step (2) being dried, powder grinds, sieves, and the PVA adding 5wt.% fully grinds and carries out granulation;
(4) shaping
Powder after step (3) granulation is put into stainless steel mould, makes at the pressure of 8MPa the disk that diameter is 20mm;
(5) binder removal
The disk of step (4) is put into sintering oven, is warming up to 500 DEG C with the temperature rise rate of 1 DEG C/min, insulation 1h carries out abundant binder removal;
(6) sinter
Disk after binder removal in step (5) is put into corundum ceramic crucible, imbeds barium carbonate powder, and cover with crucible cover, 1300 DEG C are warming up to the temperature rise rate of 5 DEG C/min, insulation 5h, is chilled to room temperature with stove, obtains xLAS/BT (x=7mol%) leadless piezoelectric ceramics;
(6) plated electrode
By the ceramics sample surface finish sintered in step (5), thickness of sample is milled to about 1mm, adopts the method for magnetron sputtering, the surface that pottery is bright and clean sputters one deck silver electrode, then the ceramics sample with electrode is put into sintering oven 500 DEG C annealing, insulation 30min;
(7) polarize
By the ceramics sample of step (6) as the 30min that polarizes in the silicone oil of 80 DEG C, wherein, polarized electric field 1kV/mm, obtains barium titanate-based lead-free piezoelectric ceramics.
The barium titanate-based lead-free piezoelectric ceramics that the present embodiment obtains has piezoelectric constant d
33value is about 340pC/N.
Embodiment 4
The preparation of the barium titanate based lead-free piezoceramic material of the ion pair doping vario-property of the present embodiment, carry out according to following steps:
(1) prepare burden:
By oxide spinel barium (BaCO
3), titanium dioxide (TiO
2), Lithium Oxide 98min (Li
2o), aluminium sesquioxide (Al
2o
3) and silicon-dioxide (SiO
2), stoichiometrically Ba
1-x(Li
0.5al
0.5)
xti
1-xsi
xo
3weigh; Wherein, x=7mol%;
(2) ball milling:
The raw material that step (1) weighs is put into ball grinder, and ball-milling medium is dehydrated alcohol and zirconium oxide balls, and wherein, ball milling condition is: ratio of grinding media to material is 5:1, and rotating speed is 350r/min, and Ball-milling Time is 12h; After ball milling, ball milling gained slurry is incubated at 80 DEG C and dries 12h;
(3) pre-burning:
Corundum ceramic crucible put into by powder after step 2 being dried, is warming up to 1200 DEG C with the temperature rise rate of 5 DEG C/min, insulation 3h;
(4) secondary ball milling:
Powder after step (3) pre-burning is put into ball grinder again, and ball-milling medium is dehydrated alcohol and zirconium oxide balls, and rotating speed is 350r/min, Ball-milling Time 12h.After ball milling, ball milling gained slurry is incubated at 80 DEG C and dries 12h;
(5) granulation
After step (4) being dried, powder grinds, sieves, and then adds the abundant grinding of 5wt.% polyvinyl alcohol (Polyvinyl Alcohol, PVA) and carries out granulation;
(6) shaping
Powder after step (5) granulation is put into mould, makes disk at the pressure of 10MPa;
(7) binder removal
The disk of step (6) is put into sintering oven, is warming up to 500 DEG C with the temperature rise rate of 1 DEG C/min, insulation 1h carries out binder removal;
(8) sinter
Disk after binder removal in step (7) is put in corundum ceramic crucible (this needs to limit, because corundum is high temperature resistant), imbed barium carbonate powder, 1350 DEG C are warming up to the temperature rise rate of 5 DEG C/min, insulation 2h, is chilled to room temperature with stove, obtains Ba
1-x(Li
0.5al
0.5)
xti
1-0.5xsi
0.5xo
3leadless piezoelectric ceramics;
(9) plated electrode
By the leadless piezoelectric ceramics surface finish obtained in step (8), adopt the method for magnetron sputtering, ceramic plate upper and lower surface after a polish sputters one deck silver electrode; Then the leadless piezoelectric ceramics with electrode is put into sintering oven to anneal under temperature is 500 DEG C of conditions, insulation 30min;
(10) polarize
Leadless piezoelectric ceramics after step (9) being sintered is the 30min that polarizes in the silicone oil of 80 DEG C as temperature, wherein, and polarized electric field 3kV/mm.
The barium titanate-based lead-free piezoelectric ceramics that the present embodiment obtains has piezoelectric constant d
33value is about 350pC/N.
Embodiment 5
The preparation of the barium titanate based lead-free piezoceramic material of the ion pair doping vario-property of the present embodiment, carry out according to following steps:
(1) prepare burden:
By oxide spinel barium (BaCO
3), titanium dioxide (TiO
2), Lithium Oxide 98min (Li
2o), aluminium sesquioxide (Al
2o
3) and silicon-dioxide (SiO
2), stoichiometrically Ba
1-x(Li
0.5al
0.5)
xti
1-xsi
xo
3weigh; Wherein, x=5mol%;
(2) ball milling:
The raw material that step (1) weighs is put into ball grinder, and ball-milling medium is dehydrated alcohol and zirconium oxide balls, and wherein, ball milling condition is: ratio of grinding media to material is 5:1, and rotating speed is 300r/min, and Ball-milling Time is 10h; After ball milling, ball milling gained slurry is incubated at 80 DEG C and dries 12h;
(3) pre-burning:
Corundum ceramic crucible put into by powder after step 2 being dried, is warming up to 1250 DEG C with the temperature rise rate of 5 DEG C/min, insulation 2h;
(4) secondary ball milling:
Powder after step (3) pre-burning is put into ball grinder again, and ball-milling medium is dehydrated alcohol and zirconium oxide balls, and rotating speed is 300r/min, Ball-milling Time 10h.After ball milling, ball milling gained slurry is incubated at 80 DEG C and dries 12h;
(5) granulation
After step (4) being dried, powder grinds, sieves, and then adds the abundant grinding of 5wt.% polyvinyl alcohol (Polyvinyl Alcohol, PVA) and carries out granulation;
(6) shaping
Powder after step (5) granulation is put into mould, makes disk at the pressure of 10MPa;
(7) binder removal
The disk of step (6) is put into sintering oven, is warming up to 500 DEG C with the temperature rise rate of 1 DEG C/min, insulation 1h carries out binder removal;
(8) sinter
Disk after binder removal in step (7) is put in corundum ceramic crucible (this needs to limit, because corundum is high temperature resistant), imbed barium carbonate powder, 1350 DEG C are warming up to the temperature rise rate of 5 DEG C/min, insulation 2h, is chilled to room temperature with stove, obtains Ba
1-x(Li
0.5al
0.5)
xti
1-0.5xsi
0.5xo
3leadless piezoelectric ceramics;
(9) plated electrode
By the leadless piezoelectric ceramics surface finish obtained in step (8), adopt the method for magnetron sputtering, ceramic plate upper and lower surface after a polish sputters one deck silver electrode; Then the leadless piezoelectric ceramics with electrode is put into sintering oven to anneal under temperature is 500 DEG C of conditions, insulation 30min;
(10) polarize
Leadless piezoelectric ceramics after step (9) being sintered is the 30min that polarizes in the silicone oil of 80 DEG C as temperature, wherein, and polarized electric field 3kV/mm.
The barium titanate-based lead-free piezoelectric ceramics that the present embodiment obtains has piezoelectric constant d
33value is about 340pC/N.
Embodiment 6
The preparation of the barium titanate based lead-free piezoceramic material of the ion pair doping vario-property of the present embodiment, carry out according to following steps:
(1) prepare burden
By oxide spinel barium (BaCO
3), titanium dioxide (TiO
2) stoichiometrically Ba/Ti=1:1 prepare;
(2) ball milling
Step (1) load weighted raw material is put into ball grinder, and ball-milling medium is dehydrated alcohol and zirconium oxide balls, and ratio of grinding media to material is 4:1, rotating speed 350r/min, ball milling 18h, and ball milling gained slurry is incubated at 80 DEG C dries 10h;
(3) pre-burning
Powder after step (2) being sieved, as in crucible, is warming up to 1150 DEG C with the temperature rise rate of 5 DEG C/min, and insulation 5h, then furnace cooling, obtain barium titanate (BaTiO
3) powder;
(4) secondary ball milling
By the barium carbonate powder obtained after step (3) pre-burning and eucryptite powder stoichiometrically xLAS/BT (x=6mol%) prepare, ball-milling medium is dehydrated alcohol and zirconium oxide balls, ratio of grinding media to material is 5:1, rotating speed 350r/min, ball milling 10h, ball milling gained slurry is incubated at 80 DEG C dries 10h;
(5) granulation
After step (4) being dried, powder grinds, sieves, and the PVA adding 5wt.% fully grinds and carries out granulation;
(6) shaping
Powder after step (5) granulation is put into mould, makes disk at the pressure of 8MPa;
(7) binder removal
The disk of step (6) is put into sintering oven, is warming up to 500 DEG C with the temperature rise rate of 1 DEG C/min, insulation 1h carries out abundant binder removal;
(8) sinter
Disk after binder removal in step (7) is put into corundum ceramic crucible, imbeds barium carbonate powder, be warming up to 1350 DEG C with the temperature rise rate of 5 DEG C/min, insulation 4h, is chilled to room temperature with stove, obtains xLAS/BT leadless piezoelectric ceramics;
(9) plated electrode
By the ceramics sample surface finish sintered in step (8), adopt the method for magnetron sputtering, the surface that pottery is bright and clean sputters one deck silver electrode.Then the ceramics sample with electrode is put into sintering oven 500 DEG C annealing, insulation 30min;
(10) polarize
By the ceramics sample of step (9) as in the silicone oil of 80 DEG C, polarization 30min, polarized electric field 2kV/mm.
The barium titanate-based lead-free piezoelectric ceramics that the present embodiment obtains has piezoelectric constant d
33value is about 360pC/N.
Claims (7)
1. lithium-aluminum ion is to the preparation method of the barium titanate based lead-free piezoceramic material of doping vario-property, it is characterized in that it is prepared according to following steps:
One, prepare burden:
By raw material BaCO
3, TiO
2, Li
2o, Al
2o
3and SiO
2, stoichiometrically Ba
1-x(Li
0.5al
0.5)
xti
1-xsixO3 weighs; Wherein, x=2 ~ 8mol%;
Two, ball milling:
Ball grinder ball milling put into by raw material step one weighed, and ball-milling medium is dehydrated alcohol and zirconium oxide balls, and wherein, ball milling condition is: ratio of grinding media to material is (2 ~ 5): 1, and rotating speed is 300 ~ 350r/min, and Ball-milling Time is 6 ~ 12h; After ball milling, ball milling gained slurry is incubated oven dry 10 ~ 12h at 80 DEG C;
Three, pre-burning:
Corundum ceramic crucible put into by powder after step 2 being dried, is warming up to 1150 ~ 1250 DEG C with the temperature rise rate of 5 DEG C/min, insulation 2 ~ 5h;
Four, secondary ball milling:
Powder after step 3 pre-burning is put into ball grinder again, and ball-milling medium is dehydrated alcohol and zirconium oxide balls, and wherein, ball milling condition is: rotating speed is 300 ~ 350r/min, and Ball-milling Time is 6 ~ 12h; After ball milling, ball milling gained slurry is incubated oven dry 10 ~ 12h at 80 DEG C;
Five, granulation
After step 4 being dried, powder grinds, sieves, and then interpolation 5wt.% polyvinyl alcohol fully grinds and carries out granulation;
Six, shaping
Powder after step 5 granulation is put into mould, makes disk at the pressure of 8 ~ 10MPa;
Seven, binder removal
The disk of step 6 is put into sintering oven, is warming up to 500 DEG C with the temperature rise rate of 1 DEG C/min, insulation 1h carries out binder removal;
Eight, sinter
Disk after binder removal in step 7 is put into corundum ceramic crucible, imbeds barium carbonate powder, be warming up to 1300 ~ 1400 DEG C with the temperature rise rate of 5 DEG C/min, insulation 2 ~ 5h, is chilled to room temperature with stove, obtains Ba
1-x(Li
0.5al
0.5)
xti
1-xsixO3 leadless piezoelectric ceramics;
Nine, plated electrode
By the Ba obtained in step 8
1-x(Li
0.5al
0.5)
xti
1-xthe surface finish of SixO3 leadless piezoelectric ceramics, adopt the method for magnetron sputtering, ceramic plate upper and lower surface after a polish sputters one deck silver electrode; Then the leadless piezoelectric ceramics with electrode is put into sintering oven to anneal under temperature is 500 DEG C of conditions, insulation 30min;
Ten, polarize
Be the 30min that polarizes in the silicone oil of 80 DEG C as temperature by the leadless piezoelectric ceramics after step 9 annealing insulation, wherein, polarized electric field 1 ~ 3kV/mm, namely completes; Wherein, the chemical constitution general formula of lithium-aluminum ion to the barium titanate based lead-free piezoceramic material of doping vario-property is Ba
1-x(Li
0.5al
0.5)
xti
1-xsixO3; Described x=2 ~ 8mol%.
2. lithium-aluminum ion according to claim 1 is to the preparation method of the barium titanate based lead-free piezoceramic material of doping vario-property, it is characterized in that the x=4 ~ 6mol% described in step one.
3. lithium-aluminum ion is to the preparation method of the barium titanate based lead-free piezoceramic material of doping vario-property, it is characterized in that it is prepared according to following steps:
One, prepare burden
By raw material BaTiO
3and LiAlSiO
4stoichiometrically xLiAlSiO
4/ (1-x) BaTiO
3weigh, wherein, x=2 ~ 8mol%;
Two, ball milling
Ball grinder ball milling put into by raw material step one weighed, and ball-milling medium is dehydrated alcohol and zirconium oxide balls, and wherein, ball milling condition is: ratio of grinding media to material is (5 ~ 10): 1, and rotating speed is 300 ~ 350r/min, and Ball-milling Time is 6 ~ 12h; After ball milling, ball milling gained slurry is incubated oven dry 10 ~ 12h under temperature is 80 DEG C of conditions, then grinds, sieve, obtain powder;
Three, granulation
After step 2 being dried, powder grinds, sieves, and the polyvinyl alcohol then adding 5wt.% fully grinds and carries out granulation;
Four, shaping
Powder after step 3 granulation is put into mould, makes disk at the pressure of 8 ~ 10MPa;
Five, binder removal
The disk of step 4 is put into sintering oven, is warming up to 500 DEG C with the temperature rise rate of 1 DEG C/min, insulation 1h carries out binder removal;
Six, sinter
Disk after binder removal in step 5 is put into corundum ceramic crucible, imbeds barium carbonate powder, be warming up to 1300 ~ 1400 DEG C with the temperature rise rate of 5 DEG C/min, insulation 2 ~ 5h, is chilled to room temperature with stove, obtains xLiAlSiO
4/ (1-x) BaTiO
3lead-free piezoceramic material;
Seven, plated electrode
By the xLiAlSiO obtained in step 6
4/ (1-x) BaTiO
3lead-free piezoceramic material surface finish, adopts the method for magnetron sputtering, the surface after leadless piezoelectric ceramics polishing sputters one deck silver electrode; Then the leadless piezoelectric ceramics with electrode is put into sintering oven to anneal under temperature is 500 DEG C of conditions, insulation 30min;
Eight, polarize
Pottery after step 7 plated electrode being placed in temperature is that the silicone oil of 80 DEG C polarizes, and wherein, polarized electric field is 1 ~ 3kV/mm, and the polarization time is 30min, namely completes; Wherein, the chemical constitution general formula of lithium-aluminum ion to the barium titanate based lead-free piezoceramic material of doping vario-property is Ba
1-x(Li
0.5al
0.5)
xti
1-xsixO3; Described x=2 ~ 8mol%.
4. lithium-aluminum ion according to claim 3 is to the preparation method of the barium titanate based lead-free piezoceramic material of doping vario-property, it is characterized in that the x=4 ~ 6mol% described in step one.
5. lithium-aluminum ion is to the preparation method of the barium titanate based lead-free piezoceramic material of doping vario-property, it is characterized in that it is prepared according to following steps:
One, prepare burden
By raw material BaCO
3and TiO
2ba/Ti=1:1 weighs in molar ratio;
Two, ball milling
Load weighted for step one raw material is put into ball grinder ball milling, ball-milling medium is dehydrated alcohol and zirconium oxide balls, wherein, ball milling condition is: ratio of grinding media to material is (2 ~ 5): 1, rotating speed is 300 ~ 350r/min, Ball-milling Time is 12 ~ 24h, and ball milling gained slurry is incubated oven dry 10 ~ 12h at 80 DEG C;
Three, pre-burning
Powder after step 2 being sieved, as in crucible, is warming up to 1150 ~ 1250 DEG C with the temperature rise rate of 5 DEG C/min, and insulation 2 ~ 5h, then furnace cooling, obtain barium carbonate powder;
Four, secondary ball milling
By the barium carbonate powder that obtains after step 3 pre-burning and eucryptite powder stoichiometrically xLiAlSiO
4/ (1-x) BaTiO
3weigh, wherein, x=2 ~ 8mol%, then the barium carbonate powder taken and eucryptite powder are put into ball grinder ball milling, wherein, ball milling condition is: ball-milling medium is dehydrated alcohol and zirconium oxide balls, ratio of grinding media to material is (5 ~ 10): 1, rotating speed is 300 ~ 350r/min, and Ball-milling Time is 6 ~ 10h, and ball milling gained slurry is incubated oven dry 10 ~ 12h at 80 DEG C;
Five, granulation
After step 4 being dried, powder grinds, sieves, and the polyvinyl alcohol then adding 5wt.% fully grinds and carries out granulation;
Six, shaping
Powder after step 5 granulation is put into mould, makes disk at the pressure of 8 ~ 10MPa;
Seven, binder removal
The disk of step 6 is put into sintering oven, is warming up to 500 DEG C with the temperature rise rate of 1 DEG C/min, insulation 1h carries out abundant binder removal;
Eight, sinter
Disk after binder removal in step 7 is put into corundum ceramic crucible, imbeds barium carbonate powder, be warming up to 1300 ~ 1400 DEG C with the temperature rise rate of 5 DEG C/min, insulation 2 ~ 5h, is chilled to room temperature with stove, obtains xLiAlSiO
4/ (1-x) BaTiO
3leadless piezoelectric ceramics;
Nine, plated electrode
By the xLiAlSiO sintered in step 8
4/ (1-x) BaTiO
3leadless piezoelectric ceramics surface finish, adopts the method for magnetron sputtering, the surface that pottery is bright and clean sputters one deck silver electrode; Then the ceramics sample with electrode is put into sintering oven 500 DEG C annealing, insulation 30min;
Ten, polarize
Ceramics sample after the annealing of step 9 being incubated is placed in the silicone oil of 80 DEG C, and the polarization time is 30min, and polarized electric field is 1 ~ 3kV/mm, namely completes; Wherein, lithium-aluminum ion is to the barium titanate based lead-free piezoceramic material of doping vario-property.
6. lithium-aluminum ion according to claim 5 is to the preparation method of the barium titanate based lead-free piezoceramic material of doping vario-property, it is characterized in that the x=4 ~ 6mol% described in step 4.
7. lithium-aluminum ion according to claim 5 is to the preparation method of the barium titanate based lead-free piezoceramic material of doping vario-property, it is characterized in that, described in step 8, the disk after binder removal in step 7 is put into corundum ceramic crucible, imbed barium carbonate powder, 1350 ~ 1400 DEG C are warming up to, insulation 3 ~ 5h with the temperature rise rate of 5 DEG C/min.
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| CN109320241A (en) * | 2018-10-22 | 2019-02-12 | 西安电子科技大学 | A kind of preparation method of lithium aluminium codope hafnium lead titanates-lead nickle niobate piezoelectric ceramics |
| CN110015893A (en) * | 2019-05-20 | 2019-07-16 | 哈尔滨理工大学 | A kind of composite mixed bismuth ferrite-barium titanate binary system Lead-free ferroelectric ceramics material, preparation method and applications |
| CN110357614B (en) * | 2019-07-25 | 2021-12-10 | 哈尔滨理工大学 | Room-temperature paraelectric-ferroelectric adjustable ceramic material and preparation method thereof |
| CN110510670B (en) * | 2019-09-25 | 2022-02-22 | 河南工程学院 | One-dimensional composite material with high dielectric constant and low expansion coefficient and preparation method thereof |
| CN111548149B (en) * | 2020-05-26 | 2022-02-18 | 哈尔滨工业大学 | Barium titanate lead-free piezoelectric ceramic with high temperature stability and preparation method thereof |
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