CN103979955A - Barium titanate based leadless piezoceramic material doped and modified by lithium-aluminum ion pair and preparing method thereof - Google Patents
Barium titanate based leadless piezoceramic material doped and modified by lithium-aluminum ion pair and preparing method thereof Download PDFInfo
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- CN103979955A CN103979955A CN201410200916.1A CN201410200916A CN103979955A CN 103979955 A CN103979955 A CN 103979955A CN 201410200916 A CN201410200916 A CN 201410200916A CN 103979955 A CN103979955 A CN 103979955A
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Abstract
The invention relates to a barium titanate based leadless piezoceramic material with high piezoelectric property and a preparing method thereof, and particularly to a barium titanate based leadless piezoceramic material doped and modified by a lithium-aluminum ion pair and a preparing method thereof. 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 have high tension performance barium titanate based lead-free piezoceramic material and preparation method thereof.
Background technology
In recent years, due to leaded in Pb-based lanthanumdoped zirconate titanates (PZT) ceramic systems, in the process of preparation, use and waste treatment all easily to environment, thereby the exploitation of leadless piezoelectric ceramics is just become to inexorable trend.Barium titanate (BaTiO
3, BT) and pottery is the Lead-free ferroelectric ceramics more Zao than PZT ceramic applications.For example, the thin brilliant BT piezoelectric ceramics of preparing 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 of being prepared by common raw material and traditional solid phase synthesis process is conventionally smaller, only has 200-300pC/N.
To thering is ABO
3the ferroelectric ceramic(s) (as PZT, BT, potassium-sodium niobate (KNN) etc.) of type perovskite structure, obtain the most basic approach of large piezoelectric effect and have two kinds: the one, design accurate homotype phase boundary (MPB), as PZT system, approach Pb (Zr as dividing
0.52ti
0.48) O
3time, the phase transformation of being brought out by composition will cause PZT base pottery near MPB, to have excellent piezoelectric and dielectric properties; The 2nd, utilize many types of change mutually (PPT), as KNN system, while being down near room temperature to the phase transition temperature of Tetragonal mutually, utilize the orthogonal of temperature-driven also can produce large piezoelectric property (d to the phase transformation of Tetragonal mutually when orthogonal
33=300-400pC/N).According in found Patents, yet there are no the preparation of barium titanate-based lead-free piezoelectric ceramics and the research of piezoelectric property thereof of dopant ion to modification.
Publication number is that the patent documentation of CN102249671A (application number 201110126758.6) discloses a kind of barium titanate based lead-free piezoceramic material and preparation method thereof, and its main body component molecules 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 that accounts for main body composition 0.08～0.25wt%
2o
3with the MgO of 0.02～0.20wt%, this material has the preparation of two-step sintering method, its piezoelectric constant d
33reach 164pC/N, electromechanical coupling factor k
preach 0.348.Publication number is that the patent documentation of CN101182203A (application number 200710114644.3) discloses a kind of barium titanate based piezoelectric ceramic materials with average grain size 0.2-7.5 μ m, its piezoelectric property d of preparing by solid-phase synthesis
33value is greater than 225pC/N.Publication number is the barium phthalate base piezoelectric that the patent documentation of CN101333106A (application number 200810138722.8) discloses a kind of modification, 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 advantages of that electromechanical coupling factor is large and mechanical quality factor is high and piezoelectric property temperature is good.In these disclosed patents, the piezoelectricity level of barium titanate base piezoelectric ceramic only has 200pC/N left and right, obtains d
33>300pC/N is very difficult thing.
Summary of the invention
To the object of the invention is the poor problem of barium titanate-based lead-free piezoelectric ceramics piezoelectric property of utilizing common raw material and traditional solid-phase synthesis to prepare in order solving, lithium-aluminum ion barium titanate based lead-free piezoceramic material to doping vario-property and preparation method thereof to be provided.
The barium titanate based lead-free piezoceramic material of lithium-aluminum ion of the present invention to doping vario-property, its chemical constitution general formula is Ba
1-x(Li
0.5al
0.5)
xti
1-xsixO
3; It is by BaCO
3, TiO
2, Li
2o, Al
2o
3and SiO
2by stoichiometric ratio Ba
1-x(Li
0.5al
0.5)
xti
1-xsixO
3make, wherein, described x=2～8mol%.
The preparation method of the barium titanate based lead-free piezoceramic material of lithium-aluminum ion of the present invention to doping vario-property, prepares according to following steps:
One, batching:
By raw material BaCO
3, TiO
2, Li
2o, Al
2o
3and SiO
2, by stoichiometric ratio Ba
1-x(Li
0.5al
0.5)
xti
1-xsixO
3weigh; Wherein, x=2～8mol%;
Two, ball milling:
The raw material that step 1 is weighed is put into ball grinder ball milling, 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, Ball-milling Time is 6～12h; After ball milling, ball milling gained slurry is incubated at 80 DEG C and dries 10～12h;
Three, pre-burning:
Powder after step 2 is dried is put into corundum ceramic crucible, 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 at 80 DEG C and dries 10～12h;
Five, granulation
After step 4 is dried, powder grinds, sieves, and then adds 5wt.% polyvinyl alcohol and fully grinds and carry out granulation;
Six, moulding
Powder after step 5 granulation is put into mould, under the pressure of 8～10MPa, be pressed into disk;
Seven, binder removal
The disk of step 6 is put into sintering oven, be warming up to 500 DEG C with the temperature rise rate of 1 DEG C/min, insulation 1h carries out binder removal;
Eight, sintering
Disk after binder removal in step 7 is put into corundum ceramic crucible, imbed 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-xsixO
3leadless piezoelectric ceramics;
Nine, plated electrode
By the Ba obtaining in step 8
1-x(Li
0.5al
0.5)
xti
1-xsixO
3leadless piezoelectric ceramics surface finish, the method for employing magnetron sputtering, the ceramic plate upper and lower surface sputter one deck silver electrode after polishing; Then be to anneal under 500 DEG C of conditions put into sintering oven with the leadless piezoelectric ceramics of electrode in temperature, insulation 30min;
Ten, polarization
Be the 30min that polarizes in the silicone oil of 80 DEG C as for temperature by the leadless piezoelectric ceramics after step 7 sintering, wherein, polarized electric field 1～3kV/mm, completes.
The barium titanate based lead-free piezoceramic material of lithium-aluminum ion of the present invention to doping vario-property, its chemical constitution general formula is xLAS/BT; It is by BaTiO
3and LiAlSiO
4by stoichiometric ratio, xLAS/BT makes, wherein, and described x=2～8mol%.
The preparation method of the barium titanate based lead-free piezoceramic material of lithium-aluminum ion of the present invention to doping vario-property, prepares according to following steps:
One, batching
By raw material BaTiO
3and LiAlSiO
4by stoichiometric ratio, xLAS/BT weighs, wherein, and x=2～8mol%;
Two, ball milling
The raw material that step 1 is weighed is put into ball grinder ball milling, 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, Ball-milling Time is 6～12h; After ball milling, be that under 80 DEG C of conditions, 10～12h is dried in insulation by ball milling gained slurry in temperature, then grind, sieve, obtain powder;
Three, granulation
After step 2 is dried, powder grinds, sieves, and the polyvinyl alcohol that then adds 5wt.% fully grinds and carries out granulation;
Four, moulding
Powder after step 3 granulation is put into mould, under the pressure of 8～10MPa, be pressed into disk;
Five, binder removal
The disk of step 4 is put into sintering oven, be warming up to 500 DEG C with the temperature rise rate of 1 DEG C/min, insulation 1h carries out binder removal;
Six, sintering
Disk after binder removal in step 5 is put into corundum ceramic crucible, imbed 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 obtaining in step 6, adopt the method for magnetron sputtering, sputter one deck silver electrode on the surface after leadless piezoelectric ceramics polishing; Then be to anneal under 500 DEG C of conditions put into sintering oven with the leadless piezoelectric ceramics of electrode in temperature, insulation 30min;
Eight, polarization
It is that the silicone oil of 80 DEG C polarizes that pottery after step 7 plated electrode is placed in to temperature, and wherein, polarized electric field is 1～3kV/mm, and the polarization time is 30min, completes.
The barium titanate based lead-free piezoceramic material of lithium-aluminum ion of the present invention to doping vario-property, it is by BaCO
3and TiO
2ba/Ti=1:1 makes in molar ratio.
The preparation method of the barium titanate based lead-free piezoceramic material of lithium-aluminum ion of the present invention to doping vario-property, prepares according to following steps:
One, batching
By raw material BaCO
3and TiO
2ba/Ti=1:1 weighs in molar ratio;
Two, ball milling
Load weighted step 1 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 at 80 DEG C dries 10～12h;
Three, pre-burning
Powder after step 2 is sieved, as in crucible, is warming up to 1150～1250 DEG C with the temperature rise rate of 5 DEG C/min, insulation 2～5h, and then furnace cooling, obtains barium carbonate powder;
Four, secondary ball milling
The barium carbonate powder obtaining after step 3 pre-burning and eucryptite powder are taken by stoichiometric ratio xLAS/BT, wherein, x=2～8mol%, then the barium carbonate powder taking 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 at 80 DEG C dries 10～12h;
Five, granulation
After step 4 is dried, powder grinds, sieves, and the polyvinyl alcohol that then adds 5wt.% fully grinds and carries out granulation;
Six, moulding
Powder after step 5 granulation is put into mould, under the pressure of 8～10MPa, be pressed into disk;
Seven, binder removal
The disk of step 6 is put into sintering oven, be warming up to 500 DEG C with the temperature rise rate of 1 DEG C/min, insulation 1h carries out abundant binder removal;
Eight, sintering
Disk after binder removal in step 7 is put into corundum ceramic crucible, imbed 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 sintering in step 8, adopt the method for magnetron sputtering, sputter one deck silver electrode on the bright and clean surface of pottery; Then 500 DEG C of annealing of sintering oven will be put into the ceramics sample of electrode, insulation 30min;
Ten, polarization
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, 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
33brought up to the piezoelectric property of 300-400pC/N 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-xsixO
3, wherein 0.02≤x≤0.08mol.Prepare this material desired raw material and 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 right doping vario-property of lithium-aluminum ion, the piezoelectric property of barium titanate base piezoelectric ceramic is greatly improved.Up to the present yet there are no the report that utilizes ion pair doping vario-property to improve barium titanate-based lead-free piezoelectric ceramics piezoelectric property aspect.
Brief description of the drawings:
Fig. 1 is executing 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 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 the schematic diagram that lithium-aluminum ion affects barium titanate lattice doping;
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 that executes gained barium titanate base piezoelectric ceramic under example 1 operational condition
33) and contrary piezo-electric modulus (dS/dE) and pure barium titanate piezoelectric ceramics Performance Ratio are; Wherein,
for piezoelectric constant (d
33) graphic representation;
for the graphic representation of contrary piezo-electric modulus (dS/dE);
Fig. 6 is at the electromechanical coupling factor of 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.
Embodiment one: the barium titanate based lead-free piezoceramic material of the lithium-aluminum ion of present embodiment to doping vario-property, its chemical constitution general formula is Ba
1-x(Li
0.5al
0.5)
xti
1-xsixO
3; It is by BaCO
3, TiO
2, Li
2o, Al
2o
3and SiO
2by stoichiometric ratio Ba
1-x(Li
0.5al
0.5)
xti
1-xsixO
3make, wherein, described x=2～8mol%.
Embodiment two: present embodiment is from specifically embodiment one is different: 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
33brought up to the piezoelectric property of 300-400pC/N 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-xsixO
3, wherein 0.02≤x≤0.08mol.Up to the present yet there are no the report that utilizes ion pair doping vario-property to improve barium titanate-based lead-free piezoelectric ceramics piezoelectric property aspect.
Embodiment three: the preparation method of the barium titanate based lead-free piezoceramic material of the lithium-aluminum ion of present embodiment to doping vario-property, prepares according to following steps:
One, batching:
By raw material BaCO
3, TiO
2, Li
2o, Al
2o
3and SiO
2, by stoichiometric ratio Ba
1-x(Li
0.5al
0.5)
xti
1-xsixO
3weigh; Wherein, x=2～8mol%;
Two, ball milling:
The raw material that step 1 is weighed is put into ball grinder ball milling, 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, Ball-milling Time is 6～12h; After ball milling, ball milling gained slurry is incubated at 80 DEG C and dries 10～12h;
Three, pre-burning:
Powder after step 2 is dried is put into corundum ceramic crucible, 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 at 80 DEG C and dries 10～12h;
Five, granulation
After step 4 is dried, powder grinds, sieves, and then adds 5wt.% polyvinyl alcohol and fully grinds and carry out granulation;
Six, moulding
Powder after step 5 granulation is put into mould, under the pressure of 8～10MPa, be pressed into disk;
Seven, binder removal
The disk of step 6 is put into sintering oven, be warming up to 500 DEG C with the temperature rise rate of 1 DEG C/min, insulation 1h carries out binder removal;
Eight, sintering
Disk after binder removal in step 7 is put into corundum ceramic crucible, imbed 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-xsixO
3leadless piezoelectric ceramics;
Nine, plated electrode
By the Ba obtaining in step 8
1-x(Li
0.5al
0.5)
xti
1-xsixO
3leadless piezoelectric ceramics surface finish, the method for employing magnetron sputtering, the ceramic plate upper and lower surface sputter one deck silver electrode after polishing; Then be to anneal under 500 DEG C of conditions put into sintering oven with the leadless piezoelectric ceramics of electrode in temperature, insulation 30min;
Ten, polarization
Be the 30min that polarizes in the silicone oil of 80 DEG C as for temperature by the leadless piezoelectric ceramics after step 7 sintering, wherein, polarized electric field 1～3kV/mm, 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
33brought up to the piezoelectric property of 300-400pC/N 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-xsixO
3, wherein 0.02≤x≤0.08mol.Prepare this material desired raw material and 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 right doping vario-property of lithium-aluminum ion, the piezoelectric property of barium titanate base piezoelectric ceramic is greatly improved.Up to the present yet there are no the report that utilizes ion pair doping vario-property to improve barium titanate-based lead-free piezoelectric ceramics piezoelectric property aspect.
Embodiment four: present embodiment is from specifically embodiment three is different: the x=4～6mol% described in step 1.Other is identical with embodiment three.
Embodiment five: present embodiment is from specifically embodiment three or four is different: the x=5mol% described in step 1.Other is identical with embodiment three or four.
Embodiment six: present embodiment is from specifically one of embodiment three to five is different: the ball milling condition described in step 2 is: ratio of grinding media to material is (3～5): 1, rotating speed is 320～350r/min, Ball-milling Time is 8～12h; After ball milling, ball milling gained slurry is incubated at 80 DEG C and dries 10～12h.Other is identical with one of embodiment three to five.
Embodiment seven: present embodiment is from specifically one of embodiment three to six is different: the temperature rise rate with 5 DEG C/min described in step 3 is warming up to 1200～1250 DEG C, insulation 3～5h.Other is identical with one of embodiment three to six.
Embodiment eight: present embodiment is from specifically one of embodiment three to seven is different: the temperature rise rate with 5 DEG C/min described in step 8 is warming up to 1350～1400 DEG C, insulation 3～5h.Other is identical with one of embodiment three to seven.
Embodiment nine: present embodiment is from specifically one of embodiment three to eight is different: the polarized electric field 2kV/mm described in step 10.Other is identical with one of embodiment three to eight.
Embodiment ten: the barium titanate based lead-free piezoceramic material of the lithium-aluminum ion of present embodiment to doping vario-property, its chemical constitution general formula is xLAS/BT; It is by BaTiO
3and LiAlSiO
4by stoichiometric ratio, 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-xsixO
3, wherein 0.02≤x≤0.08mol.Up to the present yet there are no the report that utilizes ion pair doping vario-property to improve barium titanate-based lead-free piezoelectric ceramics piezoelectric property aspect.
Embodiment 11: present embodiment is from specifically embodiment ten is different: the x=4～6mol% described in step 1.Other is identical with embodiment ten.
Embodiment 12: the preparation method of the barium titanate based lead-free piezoceramic material of the lithium-aluminum ion of present embodiment to doping vario-property, prepares according to following steps:
One, batching
By raw material BaTiO
3and LiAlSiO
4by stoichiometric ratio, xLAS/BT weighs, wherein, and x=2～8mol%;
Two, ball milling
The raw material that step 1 is weighed is put into ball grinder ball milling, 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, Ball-milling Time is 6～12h; After ball milling, be that under 80 DEG C of conditions, 10～12h is dried in insulation by ball milling gained slurry in temperature, then grind, sieve, obtain powder;
Three, granulation
After step 2 is dried, powder grinds, sieves, and the polyvinyl alcohol that then adds 5wt.% fully grinds and carries out granulation;
Four, moulding
Powder after step 3 granulation is put into mould, under the pressure of 8～10MPa, be pressed into disk;
Five, binder removal
The disk of step 4 is put into sintering oven, be warming up to 500 DEG C with the temperature rise rate of 1 DEG C/min, insulation 1h carries out binder removal;
Six, sintering
Disk after binder removal in step 5 is put into corundum ceramic crucible, imbed 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 obtaining in step 6, adopt the method for magnetron sputtering, sputter one deck silver electrode on the surface after leadless piezoelectric ceramics polishing; Then be to anneal under 500 DEG C of conditions put into sintering oven with the leadless piezoelectric ceramics of electrode in temperature, insulation 30min;
Eight, polarization
It is that the silicone oil of 80 DEG C polarizes that pottery after step 7 plated electrode is placed in to temperature, and wherein, polarized electric field is 1～3kV/mm, and the polarization time is 30min, 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
33brought up to the piezoelectric property of 300-400pC/N 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-xsixO
3, wherein 0.02≤x≤0.08mol.Prepare this material desired raw material and 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 right doping vario-property of lithium-aluminum ion, the piezoelectric property of barium titanate base piezoelectric ceramic is greatly improved.Up to the present yet there are no the report that utilizes ion pair doping vario-property to improve barium titanate-based lead-free piezoelectric ceramics piezoelectric property aspect.
Embodiment 13: present embodiment is from specifically embodiment 12 is different: the x=4～6mol% described in step 1.Other is identical with embodiment 12.
Embodiment 14: present embodiment is from specifically embodiment 12 or 13 is different: the x=5mol% described in step 1.Other is identical with embodiment 12 or 13.
Embodiment 15: present embodiment is from specifically one of embodiment 12 to 14 is different: the ball milling condition described in step 2 is: ratio of grinding media to material is (3～5): 1, rotating speed is 320～350r/min, Ball-milling Time is 8～12h; After ball milling, ball milling gained slurry is incubated at 80 DEG C and dries 10～12h.Other is identical with one of embodiment 12 to 14.
Embodiment 16: present embodiment is from specifically one of embodiment 12 to 15 is different: the temperature rise rate with 5 DEG C/min described in step 6 is warming up to 1350～1400 DEG C, insulation 3～5h.Other is identical with one of embodiment 12 to 15.
Embodiment 17: present embodiment is from specifically one of embodiment 12 to 16 is different: the polarized electric field 2kV/mm described in step 8.Other is identical with one of embodiment 12 to 16.
Embodiment 18: the barium titanate based lead-free piezoceramic material of the lithium-aluminum ion of present embodiment to doping vario-property, 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-xsixO
3, wherein 0.02≤x≤0.08mol.Up to the present yet there are no the report that utilizes ion pair doping vario-property to improve barium titanate-based lead-free piezoelectric ceramics piezoelectric property aspect.
Embodiment 19: the preparation method of the barium titanate based lead-free piezoceramic material of the lithium-aluminum ion of present embodiment to doping vario-property, prepares according to following steps:
One, batching
By raw material BaCO
3and TiO
2ba/Ti=1:1 weighs in molar ratio;
Two, ball milling
Load weighted step 1 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 at 80 DEG C dries 10～12h;
Three, pre-burning
Powder after step 2 is sieved, as in crucible, is warming up to 1150～1250 DEG C with the temperature rise rate of 5 DEG C/min, insulation 2～5h, and then furnace cooling, obtains barium carbonate powder;
Four, secondary ball milling
The barium carbonate powder obtaining after step 3 pre-burning and eucryptite powder are taken by stoichiometric ratio xLAS/BT, wherein, x=2～8mol%, then the barium carbonate powder taking 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 at 80 DEG C dries 10～12h;
Five, granulation
After step 4 is dried, powder grinds, sieves, and the polyvinyl alcohol that then adds 5wt.% fully grinds and carries out granulation;
Six, moulding
Powder after step 5 granulation is put into mould, under the pressure of 8～10MPa, be pressed into disk;
Seven, binder removal
The disk of step 6 is put into sintering oven, be warming up to 500 DEG C with the temperature rise rate of 1 DEG C/min, insulation 1h carries out abundant binder removal;
Eight, sintering
Disk after binder removal in step 7 is put into corundum ceramic crucible, imbed 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 sintering in step 8, adopt the method for magnetron sputtering, sputter one deck silver electrode on the bright and clean surface of pottery; Then 500 DEG C of annealing of sintering oven will be put into the ceramics sample of electrode, insulation 30min;
Ten, polarization
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, 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
33brought up to the piezoelectric property of 300-400pC/N 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-xsixO
3, wherein 0.02≤x≤0.08mol.Prepare this material desired raw material and 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 right doping vario-property of lithium-aluminum ion, the piezoelectric property of barium titanate base piezoelectric ceramic is greatly improved.Up to the present yet there are no the report that utilizes ion pair doping vario-property to improve barium titanate-based lead-free piezoelectric ceramics piezoelectric property aspect.
Embodiment 20: present embodiment is from specifically embodiment 19 is different: the ball milling condition described in step 2 and four is: ratio of grinding media to material is (3～5): 1, rotating speed is 320～350r/min, Ball-milling Time is 8～12h; After ball milling, ball milling gained slurry is incubated at 80 DEG C and dries 10～12h.Other is identical with embodiment 19.
Embodiment 21: present embodiment is from specifically embodiment 19 or 20 is different: the temperature rise rate with 5 DEG C/min described in step 3 is warming up to 1200～1250 DEG C, insulation 3～5h.Other is identical with embodiment 19 or 20.
Embodiment 22: present embodiment is from specifically one of embodiment 19 to 21 is different: the temperature rise rate with 5 DEG C/min described in step 8 is warming up to 1350～1400 DEG C, insulation 3～5h.Other is identical with one of embodiment 19 to 21.
Embodiment 23: present embodiment is from specifically one of embodiment 19 to 22 is different: the polarized electric field 2kV/mm described in step 10.Other is identical with one of embodiment 19 to 22.
Verify beneficial effect of the present invention 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) batching
By raw material barium titanate (BaTiO
3, BT), eucryptite (LiAlSiO
4, LAS) weigh by stoichiometric ratio xLAS/BT (x=7.5mol%);
(2) ball milling
The load weighted raw material of step (1) 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) is dried, powder grinds, sieves, and the PVA that adds 5wt.% fully grinds and carries out granulation;
(4) moulding
Powder after step (3) granulation is put into stainless steel mould, under the pressure of 10MPa, be pressed into the disk that diameter is 10mm;
(5) binder removal
The disk of step (4) is put into sintering oven, be warming up to 500 DEG C with the temperature rise rate of 1 DEG C/min, insulation 1h carries out abundant binder removal;
(6) sintering
Disk after binder removal in step (5) is put into corundum ceramic crucible, imbed barium carbonate powder, and cover with crucible cover, be warming up to 1350 DEG C with 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 sintering in step (5), thickness of sample is milled to about 1mm, adopts the method for magnetron sputtering, sputter one deck silver electrode on the bright and clean surface of pottery, then 500 DEG C of annealing of sintering oven will be put into the ceramics sample of electrode, insulation 30min;
(7) polarization
By the ceramics sample of step (6), as for 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 has provided under the condition of the present embodiment, i.e. the XRD figure of barium titanate base piezoelectric ceramic sintering 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+ion doping has entered the A position in BT and has replaced 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+ion doping has entered the B position in BT and has replaced Ti
4+.In addition, because Li
+and Al
3+average ion radius ratio 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 the impact of tetragonality (c/a) 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 not obvious, result cause its tetragonality (c/a) decline very fast.
Fig. 4 has provided under the condition of the present embodiment, the SEM figure of barium titanate base piezoelectric ceramic, and ceramics sample sintering is dense as seen, no significant defect.
Fig. 5 has provided under the condition of the present embodiment, and the piezoelectric constant of barium titanate base piezoelectric ceramic and contrary piezo-electric modulus are visible, in the time of x=7.5mol%, and the piezoelectric constant d of ceramics sample
33value is about 378pC/N, and contrary piezoelectric coefficient d S/dE is 540pm/V.
Fig. 6 has provided 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, the piezoelectric property of the barium titanate based lead-free piezoceramic material by lithium-aluminum ion to doping vario-property has significant improvement.
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) batching
By raw material barium titanate (BaTiO
3), eucryptite (LiAlSiO
4) prepare by stoichiometric ratio xLAS/BT (x=4mol%);
(2) ball milling
The load weighted raw material of step (1) 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, and ball milling 8h, ball milling gained slurry is incubated at 80 DEG C dries 10h;
(3) granulation
After step (2) is dried, powder grinds, sieves, and the PVA that adds 5wt.% fully grinds and carries out granulation;
(4) moulding
Powder after step (3) granulation is put into stainless steel mould, under the pressure of 10MPa, be pressed into the disk that diameter is 10mm;
(5) binder removal
The disk of step (4) is put into sintering oven, be warming up to 500 DEG C with the temperature rise rate of 1 DEG C/min, insulation 1h carries out abundant binder removal;
(6) sintering
Disk after binder removal in step (5) is put into corundum ceramic crucible, imbed barium carbonate powder, and cover with crucible cover, be warming up to 1400 DEG C with 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 sintering in step (5), thickness of sample is milled to about 1mm, adopts the method for magnetron sputtering, sputter one deck silver electrode on the bright and clean surface of pottery, then 500 DEG C of annealing of sintering oven will be put into the ceramics sample of electrode, insulation 30min;
(7) polarization
By the ceramics sample of step (6), as for 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 makes 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) batching
By raw material barium titanate (BaTiO
3), eucryptite (LiAlSiO
4) prepare by stoichiometric ratio xLAS/BT (x=7mol%);
(2) ball milling
The load weighted raw material of step (1) 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, and ball milling 6h, ball milling gained slurry is incubated at 80 DEG C dries 10h;
(3) granulation
After step (2) is dried, powder grinds, sieves, and the PVA that adds 5wt.% fully grinds and carries out granulation;
(4) moulding
Powder after step (3) granulation is put into stainless steel mould, under the pressure of 8MPa, be pressed into the disk that diameter is 20mm;
(5) binder removal
The disk of step (4) is put into sintering oven, be warming up to 500 DEG C with the temperature rise rate of 1 DEG C/min, insulation 1h carries out abundant binder removal;
(6) sintering
Disk after binder removal in step (5) is put into corundum ceramic crucible, imbed barium carbonate powder, and cover with crucible cover, be warming up to 1300 DEG C with 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 sintering in step (5), thickness of sample is milled to about 1mm, adopts the method for magnetron sputtering, sputter one deck silver electrode on the bright and clean surface of pottery, then 500 DEG C of annealing of sintering oven will be put into the ceramics sample of electrode, insulation 30min;
(7) polarization
By the ceramics sample of step (6), as for 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 makes 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) batching:
By raw material barium carbonate (BaCO
3), titanium dioxide (TiO
2), Lithium Oxide 98min (Li
2o), aluminium sesquioxide (Al
2o
3) and silicon-dioxide (SiO
2), by stoichiometric ratio Ba
1-x(Li
0.5al
0.5)
xti
1-xsixO
3weigh; Wherein, x=7mol%;
(2) ball milling:
The raw material that step (1) is weighed 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:
Powder after step 2 is dried is put into corundum ceramic crucible, 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) is dried, powder grinds, sieves, and then adds 5wt.% polyvinyl alcohol (Polyvinyl Alcohol, PVA) and fully grinds and carry out granulation;
(6) moulding
Powder after step (5) granulation is put into mould, under the pressure of 10MPa, be pressed into disk;
(7) binder removal
The disk of step (6) is put into sintering oven, be warming up to 500 DEG C with the temperature rise rate of 1 DEG C/min, insulation 1h carries out binder removal;
(8) sintering
Disk after binder removal in step (7) is put in corundum ceramic crucible (this needs to limit, because corundum is high temperature resistant), imbedded barium carbonate powder, be warming up to 1350 DEG C with 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 obtaining in step (8), adopt the method for magnetron sputtering, the ceramic plate upper and lower surface sputter one deck silver electrode after polishing; Then be to anneal under 500 DEG C of conditions put into sintering oven with the leadless piezoelectric ceramics of electrode in temperature, insulation 30min;
(10) polarization
Be the 30min that polarizes in the silicone oil of 80 DEG C as for temperature by the leadless piezoelectric ceramics after step (9) sintering, wherein, polarized electric field 3kV/mm.
The barium titanate-based lead-free piezoelectric ceramics that the present embodiment makes 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) batching:
By raw material barium carbonate (BaCO
3), titanium dioxide (TiO
2), Lithium Oxide 98min (Li
2o), aluminium sesquioxide (Al
2o
3) and silicon-dioxide (SiO
2), by stoichiometric ratio Ba
1-x(Li
0.5al
0.5)
xti
1-xsixO
3weigh; Wherein, x=5mol%;
(2) ball milling:
The raw material that step (1) is weighed 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:
Powder after step 2 is dried is put into corundum ceramic crucible, 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) is dried, powder grinds, sieves, and then adds 5wt.% polyvinyl alcohol (Polyvinyl Alcohol, PVA) and fully grinds and carry out granulation;
(6) moulding
Powder after step (5) granulation is put into mould, under the pressure of 10MPa, be pressed into disk;
(7) binder removal
The disk of step (6) is put into sintering oven, be warming up to 500 DEG C with the temperature rise rate of 1 DEG C/min, insulation 1h carries out binder removal;
(8) sintering
Disk after binder removal in step (7) is put in corundum ceramic crucible (this needs to limit, because corundum is high temperature resistant), imbedded barium carbonate powder, be warming up to 1350 DEG C with 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 obtaining in step (8), adopt the method for magnetron sputtering, the ceramic plate upper and lower surface sputter one deck silver electrode after polishing; Then be to anneal under 500 DEG C of conditions put into sintering oven with the leadless piezoelectric ceramics of electrode in temperature, insulation 30min;
(10) polarization
Be the 30min that polarizes in the silicone oil of 80 DEG C as for temperature by the leadless piezoelectric ceramics after step (9) sintering, wherein, polarized electric field 3kV/mm.
The barium titanate-based lead-free piezoelectric ceramics that the present embodiment makes 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) batching
By raw material barium carbonate (BaCO
3), titanium dioxide (TiO
2) prepare by stoichiometric ratio Ba/Ti=1:1;
(2) ball milling
The load weighted raw material of step (1) 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, and ball milling 18h, ball milling gained slurry is incubated at 80 DEG C dries 10h;
(3) pre-burning
Powder after step (2) is sieved, as in crucible, is warming up to 1150 DEG C with the temperature rise rate of 5 DEG C/min, insulation 5h, and then furnace cooling, obtains barium titanate (BaTiO
3) powder;
(4) secondary ball milling
The barium carbonate powder obtaining after step (3) pre-burning and eucryptite powder are prepared by stoichiometric ratio xLAS/BT (x=6mol%), 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) is dried, powder grinds, sieves, and the PVA that adds 5wt.% fully grinds and carries out granulation;
(6) moulding
Powder after step (5) granulation is put into mould, under the pressure of 8MPa, be pressed into disk;
(7) binder removal
The disk of step (6) is put into sintering oven, be warming up to 500 DEG C with the temperature rise rate of 1 DEG C/min, insulation 1h carries out abundant binder removal;
(8) sintering
Disk after binder removal in step (7) is put into corundum ceramic crucible, imbed 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 sintering in step (8), adopt the method for magnetron sputtering, sputter one deck silver electrode on the bright and clean surface of pottery.Then 500 DEG C of annealing of sintering oven will be put into the ceramics sample of electrode, insulation 30min;
(10) polarization
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 makes has piezoelectric constant d
33value is about 360pC/N.
Claims (10)
1. the barium titanate based lead-free piezoceramic material of lithium-aluminum ion to doping vario-property, the chemical constitution general formula that it is characterized in that it is Ba
1-x(Li
0.5al
0.5)
xti
1-xsixO
3; It is by BaCO
3, TiO
2, Li
2o, Al
2o
3and SiO
2by stoichiometric ratio Ba
1-x(Li
0.5al
0.5)
xti
1-xsixO
3make, wherein, described x=2～8mol%.
2. the preparation method of the barium titanate based lead-free piezoceramic material of lithium-aluminum ion to doping vario-property, is characterized in that it prepares according to following steps:
One, batching:
By raw material BaCO
3, TiO
2, Li
2o, Al
2o
3and SiO
2, by stoichiometric ratio Ba
1-x(Li
0.5al
0.5)
xti
1-xsixO
3weigh; Wherein, x=2～8mol%;
Two, ball milling:
The raw material that step 1 is weighed is put into ball grinder ball milling, 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, Ball-milling Time is 6～12h; After ball milling, ball milling gained slurry is incubated at 80 DEG C and dries 10～12h;
Three, pre-burning:
Powder after step 2 is dried is put into corundum ceramic crucible, 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 at 80 DEG C and dries 10～12h;
Five, granulation
After step 4 is dried, powder grinds, sieves, and then adds 5wt.% polyvinyl alcohol and fully grinds and carry out granulation;
Six, moulding
Powder after step 5 granulation is put into mould, under the pressure of 8～10MPa, be pressed into disk;
Seven, binder removal
The disk of step 6 is put into sintering oven, be warming up to 500 DEG C with the temperature rise rate of 1 DEG C/min, insulation 1h carries out binder removal;
Eight, sintering
Disk after binder removal in step 7 is put into corundum ceramic crucible, imbed 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-xsixO
3leadless piezoelectric ceramics;
Nine, plated electrode
By the Ba obtaining in step 8
1-x(Li
0.5al
0.5)
xti
1-xsixO
3leadless piezoelectric ceramics surface finish, the method for employing magnetron sputtering, the ceramic plate upper and lower surface sputter one deck silver electrode after polishing; Then be to anneal under 500 DEG C of conditions put into sintering oven with the leadless piezoelectric ceramics of electrode in temperature, insulation 30min;
Ten, polarization
Be the 30min that polarizes in the silicone oil of 80 DEG C as for temperature by the leadless piezoelectric ceramics after step 7 sintering, wherein, polarized electric field 1～3kV/mm, completes.
3. the preparation method of the barium titanate based lead-free piezoceramic material of lithium-aluminum ion according to claim 2 to doping vario-property, is characterized in that the x=4～6mol% described in step 1.
4. the barium titanate based lead-free piezoceramic material of lithium-aluminum ion to doping vario-property, the chemical constitution general formula that it is characterized in that it is xLAS/BT; It is by BaTiO
3and LiAlSiO
4by stoichiometric ratio, xLAS/BT makes, wherein, and described x=2～8mol%.
5. the preparation method of the barium titanate based lead-free piezoceramic material of lithium-aluminum ion to doping vario-property, is characterized in that it prepares according to following steps:
One, batching
By raw material BaTiO
3and LiAlSiO
4by stoichiometric ratio, xLAS/BT weighs, wherein, and x=2～8mol%;
Two, ball milling
The raw material that step 1 is weighed is put into ball grinder ball milling, 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, Ball-milling Time is 6～12h; After ball milling, be that under 80 DEG C of conditions, 10～12h is dried in insulation by ball milling gained slurry in temperature, then grind, sieve, obtain powder;
Three, granulation
After step 2 is dried, powder grinds, sieves, and the polyvinyl alcohol that then adds 5wt.% fully grinds and carries out granulation;
Four, moulding
Powder after step 3 granulation is put into mould, under the pressure of 8～10MPa, be pressed into disk;
Five, binder removal
The disk of step 4 is put into sintering oven, be warming up to 500 DEG C with the temperature rise rate of 1 DEG C/min, insulation 1h carries out binder removal;
Six, sintering
Disk after binder removal in step 5 is put into corundum ceramic crucible, imbed 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 obtaining in step 6, adopt the method for magnetron sputtering, sputter one deck silver electrode on the surface after leadless piezoelectric ceramics polishing; Then be to anneal under 500 DEG C of conditions put into sintering oven with the leadless piezoelectric ceramics of electrode in temperature, insulation 30min;
Eight, polarization
It is that the silicone oil of 80 DEG C polarizes that pottery after step 7 plated electrode is placed in to temperature, and wherein, polarized electric field is 1～3kV/mm, and the polarization time is 30min, completes.
6. the preparation method of the barium titanate based lead-free piezoceramic material of lithium-aluminum ion according to claim 5 to doping vario-property, is characterized in that the x=4～6mol% described in step 1.
7. the barium titanate based lead-free piezoceramic material of lithium-aluminum ion to doping vario-property, is characterized in that it is by BaCO
3and TiO
2ba/Ti=1:1 makes in molar ratio.
8. the preparation method of the barium titanate based lead-free piezoceramic material of lithium-aluminum ion to doping vario-property, is characterized in that it prepares according to following steps:
One, batching
By raw material BaCO
3and TiO
2ba/Ti=1:1 weighs in molar ratio;
Two, ball milling
Load weighted step 1 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 at 80 DEG C dries 10～12h;
Three, pre-burning
Powder after step 2 is sieved, as in crucible, is warming up to 1150～1250 DEG C with the temperature rise rate of 5 DEG C/min, insulation 2～5h, and then furnace cooling, obtains barium carbonate powder;
Four, secondary ball milling
The barium carbonate powder obtaining after step 3 pre-burning and eucryptite powder are taken by stoichiometric ratio xLAS/BT, wherein, x=2～8mol%, then the barium carbonate powder taking 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 at 80 DEG C dries 10～12h;
Five, granulation
After step 4 is dried, powder grinds, sieves, and the polyvinyl alcohol that then adds 5wt.% fully grinds and carries out granulation;
Six, moulding
Powder after step 5 granulation is put into mould, under the pressure of 8～10MPa, be pressed into disk;
Seven, binder removal
The disk of step 6 is put into sintering oven, be warming up to 500 DEG C with the temperature rise rate of 1 DEG C/min, insulation 1h carries out abundant binder removal;
Eight, sintering
Disk after binder removal in step 7 is put into corundum ceramic crucible, imbed 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 sintering in step 8, adopt the method for magnetron sputtering, sputter one deck silver electrode on the bright and clean surface of pottery; Then 500 DEG C of annealing of sintering oven will be put into the ceramics sample of electrode, insulation 30min;
Ten, polarization
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, completes.
9. the preparation method of the barium titanate based lead-free piezoceramic material of lithium-aluminum ion according to claim 8 to doping vario-property, is characterized in that the x=4～6mol% described in step 4.
10. the preparation method of the barium titanate based lead-free piezoceramic material of lithium-aluminum ion according to claim 8 to doping vario-property, it is characterized in that the disk by after binder removal in step 7 described in step 8 puts into corundum ceramic crucible, imbed barium carbonate powder, be warming up to 1350～1400 DEG C with the temperature rise rate of 5 DEG C/min, insulation 3～5h.
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