CN106699176A - Barium titanate-based leadless piezoelectric ceramic and preparation method and application thereof - Google Patents

Barium titanate-based leadless piezoelectric ceramic and preparation method and application thereof Download PDF

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CN106699176A
CN106699176A CN201611103908.0A CN201611103908A CN106699176A CN 106699176 A CN106699176 A CN 106699176A CN 201611103908 A CN201611103908 A CN 201611103908A CN 106699176 A CN106699176 A CN 106699176A
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incubated
ball
barium titanate
ceramic
warming
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欧阳俊
李垚
成宏卜
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SUZHOU RESEARCH INSTITUTE SHANDONG UNIVERSITY
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SUZHOU RESEARCH INSTITUTE SHANDONG UNIVERSITY
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Abstract

The invention discloses a barium titanate-based leadless piezoelectric ceramic and a preparation method and application thereof. The general formula of the ceramic is shown as (SrxBa1-x)(ZryTi1-y)O3, wherein x is larger than 0 and less than or equal to 0.1; y is larger than 0 and less than or equal to 0.1; the atom percentage content of the element Zr is 2 to 7 at%. The ceramic are prepared by burdening, mixing, pre-sintering, granulating, molding, binder removal and sintering. The barium titanate-based leadless piezoelectric ceramic provided by the invention is a ferroelectric piezoelectric ceramic which has high performance, high component stability and environmental friendliness, and shows superior piezoelectric performance in a component interval in which the doping content of Zr is 2 to 7 at%, namely, d33 is larger than 320 PC/N; moreover, a (SrxBa1-x)(ZryTi1-y)O3 ceramic prepared by a solid phase sintering method is simple in process, is low in cost, is beneficial to industrial popularization, and can be widely applied to electrode materials.

Description

A kind of barium titanate-based lead-free piezoelectric ceramics, its preparation method and application
Technical field
The present invention relates to a kind of barium titanate-based lead-free piezoelectric ceramics, its preparation method and application, belong to environmentally friendly work( Can ceramic technology field.
Background technology
Barium titanate（BaTiO3, BT）It is to study so far the most thorough as famous ferroelectricity and piezoelectric One of material, and BaTiO3Base piezoelectric ceramic has excellent electric property and environment friendly, therefore as preparation nothing at present The important candidate material of lead piezoelectric ceramics.
But, the piezoelectric property of pure barium titanate is not enough (d 33~ 190 pC/N), it is difficult to directly replace lead base ceramics, and pass through Doping adds the second constituent element or the multicomponent can to optimize its phase structure in BT, so as to improve its piezoelectric property.In recent years, Many researchs are devoted to be built near room temperature the rhombohedral phase-orthorhombic phase of barium phthalate base ferroelectric piezoelectric ceramics（R-O）, it is orthogonal Phase-Tetragonal（O-T）And Tetragonal-rhombohedral phase（T-R）Phase boundary.For example, Kalyani etc. is mixed most by barium titanate Footpath B ion, but these phase boundaries are discrete in phasor, and O-T the and R-O phase boundaries for obtaining are simultaneously discontinuous, with change of component The performance difference of ceramics is obvious.
The content of the invention
It is existing to overcome it is a primary object of the present invention to provide a kind of barium titanate-based lead-free piezoelectric ceramics and preparation method thereof There is the deficiency in technology.
To realize aforementioned invention purpose, the technical solution adopted by the present invention includes：
The embodiment of the invention provides a kind of component formula of barium titanate-based lead-free piezoelectric ceramics is（SrxBa1-x）（ZryTi1-y） O3, in formula, 0<X≤0.1,0<Y≤0.1, the atomicity percentage composition of Zr elements is 2at%-7at%.
The embodiment of the present invention additionally provides a kind of method prepared by barium titanate-based lead-free piezoelectric ceramics, and it includes following step Suddenly：
First, dispensing：
By raw material TiO2、ZrO2、BaCO3、SrCO3Powder is according to stoichiometric proportion（SrxBa1-x）（ZryTi1-y）O3Weighed, Wherein 0<X≤0.1,0< y ≤ 0.1 ；
2nd, batch mixing：
The raw material that step one is weighed is put into ball milling in ball grinder, ball-milling medium is absolute ethyl alcohol and zirconium oxide balls, wherein, ball Abrasive stick part is：Ratio of grinding media to material is 4：1：1, Ball-milling Time is 10-12h；After ball milling, by ball milling gained slurry at 80-120 DEG C Insulation drying 1h；
3rd, pre-burning：
Powder after step 2 is dried is put into ceramic crucible, and 800-900 is warming up to the heating rate of 3-5 DEG C/min DEG C, and 1-2 h are incubated, then 1150-1250 DEG C is warming up to the heating rate of 3-5 DEG C/min, and it is incubated 3-5h；
4th, granulate：
Powder grinds, sieves after step 3 is dried, and then addition 5wt.% polyvinyl alcohol is fully ground and is granulated, and takes On 140 mesh sieves and 60 mesh sieve blanking powders are standby；
5th, it is molded：
By on the mesh sieve of step 4 140 and 60 mesh sieve blanking powders are put into mould Inner, it is pressed under the pressure of 180-200MPa Sequin type；
6th, plastic removal：
The sequin of step 6 is put into sintering furnace, 550-600 DEG C, insulation are warming up to the heating rate of 4-6 DEG C/min 2-3h carries out dumping；
7th, sinter：
Disk after plastic removal in step 6 is put into ceramic crucible, with heating rate as 5 DEG C/min from room temperature to 1150-1250 DEG C, 60 min are incubated, temperature is risen to 1350-1380 DEG C in 40-50 min afterwards, be incubated 10-20 Min, then 1400 DEG C are warming up in 10-20 min, 120 min are incubated, it is cooled to room temperature with stove, obtain（SrxBa1-x）（ZryTi1-y） O3；
8th, it is silver-colored
Ceramic sequin obtained in upper step is painted into silver paste in tow sides, after drying, 600 is heated in high temperature sintering furnace DEG C, and 30 min are incubated, obtain the ceramic sequin sample with silver electrode.
In some embodiments, wet-milling is carried out to material using planetary ball mill, and planetary ball mill turns Speed is 100-500 r/min；Preferably 300 r/min.
In some embodiments, the base substrate suppressed in the step 5 is disc-shaped structure, and blank diameter is 10- 15mm；Preferably 12mm, thickness is 1-2mm.
The present invention also provides a kind of electrode material, and it includes above-mentioned barium titanate-based lead-free piezoelectric ceramics.
Compared with prior art, advantages of the present invention includes：The barium titanate-based lead-free piezoelectric ceramics that the present invention is provided is height Performance, component stability high, green ferroelectric piezoelectric ceramics, in the incorporation of Zr is interval for the component of 2at%-7at% Show excellent piezoelectric propertyd 33>320 PC/N, and prepared using solid sintering technology（SrxBa1-x）（ZryTi1-y）O3Ceramics Process is simple, low cost, beneficial to industrialization promotion.
Brief description of the drawings
During Fig. 1 is an exemplary embodiments of the invention（SrxBa1-x）（ZryTi1-y）O3The process flow diagram of ceramics；
Fig. 2 is obtained Ba in the embodiment of the present invention 10.95Sr0.05ZrxTi(1-x)O3The DSC differential thermal analysis curves of ceramics；
Fig. 3 is obtained Ba in the embodiment of the present invention 10.95Sr0.05ZrxTi(1-x)O3The design principle figure of ceramics；
Fig. 4 is obtained Ba in the embodiment of the present invention 10.95Sr0.05ZrxTi(1-x)O3The XRD of ceramics；
Fig. 5 is obtained Ba in the embodiment of the present invention 10.95Sr0.05ZrxTi(1-x)O3Temperature-composition the phasor of ceramics；
Fig. 6 is obtained Ba in the embodiment of the present invention 10.95Sr0.05ZrxTi(1-x)O3The piezoelectric property figure of ceramics.
Specific embodiment
In view of deficiency of the prior art, inventor is able to propose of the invention through studying for a long period of time and largely put into practice Technical scheme.The technical scheme, its implementation process and principle etc. will be further explained as follows.
BaTiO3Belong to ABO3 type perovskite structures, with the change of temperature, BaTiO3(BT) following phase transformation is experienced Journey：Cube paraelectric phase ← 120 DEG C → Tetragonal ← 5 DEG C → orthorhombic phase ← -80 DEG C → rhombohedral phase.The incorporation meeting of different elements The change for causing these three phase transition temperatures different.Wherein, the incorporation of Zr elements can significantly change these three phase transition temperatures, specific table It is existing：It is Curie temperature（T C）Decline, Tetragonal-orthorhombic phase phase transition temperature（T O-T）And orthorhombic phase-rhombohedral phase phase transition temperature （T O-R）Substantially rise.And the incorporation of Sr elements is rightT O-RInfluence is little, and can makeT O-TAndT CIt is declined slightly.Mixed by control Enter BaTiO3Zr and Sr content, modulate its many crystal phase transition temperature（T PPT）, it is final to obtain with change of component and connectedT O-TWithT O-RPhase boundary, obtains the non-plumbum ferroelectric piezoelectric ceramics of height component stability.
The embodiment of the invention provides a kind of component formula of barium titanate-based lead-free piezoelectric ceramics is（SrxBa1-x） （ZryTi1-y）O3, in formula, 0<X≤0.1,0<Y≤0.1, the atomicity percentage composition of Zr elements is 2at%-7at%.
The embodiment of the present invention additionally provides a kind of method prepared by barium titanate-based lead-free piezoelectric ceramics, and it includes following step Suddenly：
First, dispensing：
By raw material TiO2、ZrO2、BaCO3、SrCO3Powder is according to stoichiometric proportion（SrxBa1-x）（ZryTi1-y）O3Weighed, Wherein 0<X≤0.1,0< y ≤ 0.1 ；
2nd, batch mixing：
The raw material that step one is weighed is put into ball milling in ball grinder, ball-milling medium is absolute ethyl alcohol and zirconium oxide balls, wherein, ball Abrasive stick part is：Ratio of grinding media to material is 4：1：1, Ball-milling Time is 10-12h；After ball milling, by ball milling gained slurry at 80-120 DEG C Insulation drying 1h；
3rd, pre-burning：
Powder after step 2 is dried is put into ceramic crucible, and 800-900 is warming up to the heating rate of 3-5 DEG C/min DEG C, and 1-2 h are incubated, then 1150-1250 DEG C is warming up to the heating rate of 3-5 DEG C/min, and it is incubated 3-5h；
4th, granulate：
Powder grinds, sieves after step 3 is dried, and then addition 5wt.% polyvinyl alcohol is fully ground and is granulated, and takes On 140 mesh sieves and 60 mesh sieve blanking powders are standby；
5th, it is molded：
By on the mesh sieve of step 4 140 and 60 mesh sieve blanking powders are put into mould Inner, roundlet is pressed under the pressure of 180MPa Piece type；
6th, plastic removal：
The sequin of step 6 is put into sintering furnace, 550-600 DEG C, insulation are warming up to the heating rate of 4-6 DEG C/min 2-3h carries out dumping；
7th, sinter：
Disk after plastic removal in step 6 is put into ceramic crucible, with heating rate as 5 DEG C/min from room temperature to 1150-1250 DEG C, 60 min are incubated, temperature is risen to 1350-1380 DEG C in 40-50 min afterwards, be incubated 10-20 Min, then 1400 DEG C are warming up in 10-20 min, 120 min are incubated, it is cooled to room temperature with stove, obtain（SrxBa1-x）（ZryTi1-y） O3；
8th, it is silver-colored
Ceramic sequin obtained in upper step is painted into silver paste in tow sides, after drying, 600 is heated in high temperature sintering furnace DEG C, and 30 min are incubated, obtain the ceramic sequin sample with silver electrode.
In some embodiments, wet-milling is carried out to material using planetary ball mill, and planetary ball mill turns Speed is 100-500 r/min；Preferably 300 r/min.
In some embodiments, the base substrate suppressed in the step 5 is disc-shaped structure, and blank diameter is 10- 15mm；Preferably 12mm, thickness is 1-2mm.
The present invention also provides a kind of electrode material, and it includes above-mentioned barium titanate-based lead-free piezoelectric ceramics.
In some embodiments, the method that prepared by the barium titanate-based lead-free piezoelectric ceramics, it is comprised the following steps：
1. weighing
According to the proportioning of each element in BSZT ceramics, TiO is weighed according to 0.2 mol2（98 %）、ZrO2（99 %）、BaCO3（99 %）、SrCO3（99 %）Powder；
2. batch mixing
According to the order of " how many few many ", load weighted medicine is added into ball grinder（Abrading-ball is ZrO2）In, it is subsequently adding alcohol 60 mL, batch mixing is carried out with the h of ball mill ball milling 12；
3. discharge
After 12 h, mixed slurry is placed in air dry oven by discharging（120 ℃）The h of middle drying 1；
4. pre-burning
The powder obtained after drying is placed in 200 m in crucible and is heated to 850 DEG C, and be incubated 1 h, it is therefore an objective to make carbon therein Hydrochlorate decomposes complete, is then warming up to 1150 DEG C with 1 h again, and is incubated 4 h, makes Material synthesis for BSZT, afterwards Temperature fall Cooling；
5. granulating and forming
By pre- burned raw material, crushed by corase grind, in transferring to ball grinder, and add 45 mL absolute ethyl alcohols, ball milling 12 H, refines it.The good raw material of grinding is placed in 1 h is dried in air dry oven；
Then by dried raw material, 5 wt% PVA are added, and is well mixed it, these powder are pressed with 75 Mpa afterwards Power is granulated.Crushing in agate mortar is subsequently placed in, and is ground, the material in mortar is constantly transferred to 60 in process of lapping On mesh sieve, it is crossed 60 mesh sieves and 140 mesh sieves, clout on 60 mesh sieves is transferred in mortar and continues to grind, 140 mesh sieve blankings are stayed Make bedding and padding, back and forth several times, until without clout on 60 mesh sieves；
By 60 mesh sieve blanking on 140 mesh sieves, stainless steel mould is added to（φ=12 mm）In, it is pressed under 180 MPa pressure Type；
6. plastic removal
The sequin that upper step is obtained is heated to 600 DEG C in high temperature sintering furnace, and heating rate is 5 DEG C/min, and is incubated 2 h.Purpose is to exclude the plasticiser during granulating and forming（PVA）；
7. burn till
Ceramics are burnt till according to following temperature schedule
It is 5 DEG C/min from room temperature to 1150 DEG C with heating rate, and in this temperature 60 min, afterwards with 46 Min is warming up to 1380 DEG C from 1150 DEG C, and in the temperature 10 min, then 1400 DEG C are warming up to 10 min, and at this At a temperature of be incubated 120 min.Natural cooling in stove afterwards；
8. silver-colored
Ceramic sequin obtained in upper step is painted into silver paste in tow sides, after drying, 600 is heated in high temperature sintering furnace DEG C, and 30 min are incubated, obtain the ceramic sequin sample with silver electrode.
The method of the barium titanate-based lead-free piezoelectric ceramics that the present invention is provided, solution is existing to prepare hardly possible in barium titanate ceramics technology To obtain height component stability, the low problem of piezoelectric property.Its method and step is：
（1）Choose the polymorphic transformation phase boundary that suitable element modulates barium titanate；
（2）Ceramics are prepared using solid sintering technology.
The barium titanate ferroelectric piezoelectric ceramics prepared using the inventive method have the piezoelectricity of excellent height component stabilization Performance, when the incorporation of Zr is 6 %, its piezoelectricityd 33The PC/N of value 3300.
Below in conjunction with drawings and Examples the technical solution of the present invention is further explained explanation.
Embodiment 1
Ba0.95Sr0.05Zr0.03Ti0.97O3Ceramics are prepared by solid reaction process：
1st, dispensing：
By raw material TiO2（98 %）、ZrO2（99 %）、BaCO3（99 %）、SrCO3（99 %）Powder is according to stoichiometric proportion Ba0.95Sr0.05Zr0.03Ti0.97O3Weighed；
2nd, batch mixing：
The raw material that step one is weighed is put into ball milling in ball grinder, ball-milling medium is the mL of absolute ethyl alcohol 60 and zirconium oxide balls, Batch mixing is carried out with the h of ball mill ball milling 12, after ball milling, by ball milling gained slurry in insulation drying 1h at 120 DEG C；
3rd, pre-burning：
Powder after step 2 is dried is put into ceramic crucible, is warming up to 800 DEG C with the heating rate of 4 DEG C/min, and protect 2 h of temperature, then 1200 DEG C are warming up to the heating rate of 5 DEG C/min, and it is incubated 4h；
4th, granulate：
Powder is crushed through corase grind after step 3 is dried, and in transferring to ball grinder, and adds 45 mL absolute ethyl alcohols, ball milling 12 H, refines it, is placed in and 1 h. is dried in 100 DEG C of air dry oven, then adds 5wt.% polyvinyl alcohol and is fully ground 75 Granulated under Mpa pressure, be placed in agate mortar and crush, and ground, the material in mortar is constantly transferred to 60 in process of lapping On mesh sieve, it is crossed 60 mesh sieves and 140 mesh sieves, clout on 60 mesh sieves is transferred in mortar and continues to grind, 140 mesh sieve blankings are stayed Make bedding and padding, back and forth several times, until without clout on 60 mesh sieves；
5th, it is molded：
By on the mesh sieve of step 4 140 and 60 mesh sieve blanking powders are put into mould（φ=12 mm）Inner, under the pressure of 180MPa It is pressed into sequin type；
6th, plastic removal：
The sequin of step 6 is put into sintering furnace, 600 DEG C are warming up to the heating rate of 5 DEG C/min, insulation 3h enters Row dumping；
7th, sinter：
Disk after plastic removal in step 6 is put into ceramic crucible, is 5 DEG C/min from room temperature to 1200 with heating rate DEG C, 60 min are incubated, temperature is risen to 1380 DEG C in 50 min afterwards, 10 min are incubated, then be warming up in 10 min 1400 DEG C, 120 min are incubated, room temperature is cooled to stove, obtain Ba0.95Sr0.05Zr0.03Ti0.97O3；
8th, it is silver-colored
Ceramic sequin obtained in upper step is painted into silver paste in tow sides, after drying, 600 is heated in high temperature sintering furnace DEG C, and 30 min are incubated, obtain the ceramic sequin sample with silver electrode.
It is Ba in an exemplary embodiments of the invention referring to Fig. 10.95Sr0.05ZrxTi(1-x)O3The process flow diagram of ceramics.
It is obtained Ba in the embodiment of the present invention 1 referring to Fig. 20.95Sr0.05ZrxTi(1-x)O3The DSC differential thermal analysis curves of ceramics, DSC heat analysis datas according to barium titanate synthetic reaction, there is an endothermic temperature scope wider at 600 DEG C in the past, were that there occurs Sloughing for water, is leaving away for Free water during low temperature, is then sloughing with reference to water in higher temperature；On baseline near 830 DEG C There is a significant endothermic peak, mainly there occurs the decomposition of carbonate, i.e. BaCO3And SrCO3Decompose；Have individual aobvious near 1030 DEG C The exothermic peak of work, is BaTiO3Synthesis.
Fig. 3 is obtained Ba in the embodiment of the present invention 10.95Sr0.05ZrxTi(1-x)O3The design principle figure of ceramics.Doped with The transformation behavior of different element barium titanate ceramics：（a）It is a big B ion, such as zirconium (Zr), tin (Sn) and hafnium (Hf), （b）It is a kind of slightly smaller A ion, such as strontium (Sr),（c）It is a kind of smaller A ion, such as calcium (Ca),（d）For one kind is larger A ion, such as lead (Pb);（e）B larger ion and the codope of A slightly smaller ion are acted on and cause two phase in version Region is more nearly.
It is obtained Ba in the embodiment of the present invention 1 referring to Fig. 40.95Sr0.05ZrxTi(1-x)O3The XRD of ceramics.
It is obtained Ba in the embodiment of the present invention 1 referring to Fig. 50.95Sr0.05ZrxTi(1-x)O3Temperature-composition the phasor of ceramics.
It is obtained Ba in the embodiment of the present invention 1 referring to Fig. 60.95Sr0.05ZrxTi(1-x)O3The piezoelectric property figure of ceramics, takes off The present embodiment Ba is shown0.95Sr0.05Zr0.03Ti0.97O3Ceramic machinery quality factor (Q m), electromechanical coupling factor (k p) and pressure Electrostrictive coefficient (d 33)-zirconium (Zr) relation with contents figure.
Embodiment 2
Ba0.95Sr0.05Zr0.05Ti0.95O3Ceramics are prepared by solid reaction process：
1st, dispensing：
By raw material TiO2（98 %）、ZrO2（99 %）、BaCO3（99 %）、SrCO3（99 %）Powder is according to stoichiometric proportion Ba0.95Sr0.05Zr0.05Ti0.95O3Weighed；
2nd, batch mixing：
The raw material that step one is weighed is put into ball milling in ball grinder, ball-milling medium is the mL of absolute ethyl alcohol 60 and zirconium oxide balls, Batch mixing is carried out with the h of ball mill ball milling 12, after ball milling, by ball milling gained slurry in insulation drying 1h at 120 DEG C；
3rd, pre-burning：
Powder after step 2 is dried is put into ceramic crucible, is warming up to 800 DEG C with the heating rate of 5 DEG C/min, and protect Warm 1-2 h, then 1250 DEG C are warming up to the heating rate of 5 DEG C/min, and it is incubated 5h；
4th, granulate：
Powder is crushed through corase grind after step 3 is dried, and in transferring to ball grinder, and adds 45 mL absolute ethyl alcohols, ball milling 12 H, refines it, is placed in and 1 h. is dried in 100 DEG C of air dry oven, then adds 5wt.% polyvinyl alcohol and is fully ground 75 Granulated under Mpa pressure, be placed in agate mortar and crush, and ground, the material in mortar is constantly transferred to 60 in process of lapping On mesh sieve, it is crossed 60 mesh sieves and 140 mesh sieves, clout on 60 mesh sieves is transferred in mortar and continues to grind, 140 mesh sieve blankings are stayed Make bedding and padding, back and forth several times, until without clout on 60 mesh sieves.
5th, it is molded：
By on the mesh sieve of step 4 140 and 60 mesh sieve blanking powders are put into mould（φ=12 mm）Inner, under the pressure of 180MPa It is pressed into sequin type；
6th, plastic removal：
The sequin of step 6 is put into sintering furnace, 550 DEG C are warming up to the heating rate of 4-6 DEG C/min, be incubated 2h Carry out dumping；
7th, sinter：
Disk after plastic removal in step 6 is put into ceramic crucible, is 5 DEG C/min from room temperature to 1150 with heating rate DEG C, 60 min are incubated, temperature is risen to 1350 DEG C in 50 min afterwards, 20 min are incubated, then 1400 are warming up in 20 min DEG C, 120 min are incubated, it is cooled to room temperature with stove, obtain Ba0.95Sr0.05Zr0.05Ti0.95O3。
8th, it is silver-colored
Ceramic sequin obtained in upper step is painted into silver paste in tow sides, after drying, 600 is heated in high temperature sintering furnace DEG C, and 30 min are incubated, obtain the ceramic sequin sample with silver electrode.
Embodiment 3
Ba0.95Sr0.05Zr0.06Ti0.94O3Ceramics are prepared by solid reaction process：
1st, dispensing：
By raw material TiO2（98 %）、ZrO2（99 %）、BaCO3（99 %）、SrCO3（99 %）Powder is according to stoichiometric proportion Ba0.95Sr0.05Zr0.06Ti0.94O3Weighed；
2nd, batch mixing：
The raw material that step one is weighed is put into ball milling in ball grinder, ball-milling medium is the mL of absolute ethyl alcohol 60 and zirconium oxide balls, Batch mixing is carried out with the h of ball mill ball milling 12, after ball milling, by ball milling gained slurry in insulation drying 1h at 120 DEG C；
3rd, pre-burning：
Powder after step 2 is dried is put into ceramic crucible, and 800-900 is warming up to the heating rate of 3-5 DEG C/min DEG C, and 1-2 h are incubated, then 1150-1250 DEG C is warming up to the heating rate of 3-5 DEG C/min, and it is incubated 3-5h；
4th, granulate：
Powder is crushed through corase grind after step 3 is dried, and in transferring to ball grinder, and adds 45 mL absolute ethyl alcohols, ball milling 12 H, refines it, is placed in and 1 h. is dried in 80 DEG C of air dry oven, then adds 5wt.% polyvinyl alcohol and is fully ground 75 Granulated under Mpa pressure, be placed in agate mortar and crush, and ground, the material in mortar is constantly transferred to 60 in process of lapping On mesh sieve, it is crossed 60 mesh sieves and 140 mesh sieves, clout on 60 mesh sieves is transferred in mortar and continues to grind, 140 mesh sieve blankings are stayed Make bedding and padding, back and forth several times, until without clout on 60 mesh sieves.
5th, it is molded：
By on the mesh sieve of step 4 140 and 60 mesh sieve blanking powders are put into mould（φ=12 mm）Inner, under the pressure of 180MPa It is pressed into sequin type；
6th, plastic removal：
The sequin of step 6 is put into sintering furnace, 600 DEG C are warming up to the heating rate of 6 DEG C/min, insulation 2h enters Row dumping；
7th, sinter：
Disk after plastic removal in step 6 is put into ceramic crucible, with heating rate as 5 DEG C/min from room temperature to 1150-1250 DEG C, 60 min are incubated, temperature is risen to 1350 DEG C in 45 min afterwards, be incubated 10 min, then in 10 min 1400 DEG C are warming up to, 120 min are incubated, room temperature is cooled to stove, obtain Ba0.95Sr0.05Zr0.06Ti0.94O3。
8th, it is silver-colored
Ceramic sequin obtained in upper step is painted into silver paste in tow sides, after drying, 600 is heated in high temperature sintering furnace DEG C, and 30 min are incubated, obtain the ceramic sequin sample with silver electrode.
Comparative example 1：
Ba0.95Sr0.05Zr0.01Ti0.99O3Ceramics are prepared by solid reaction process：
1st, dispensing：
By raw material TiO2（98 %）、ZrO2（99 %）、BaCO3（99 %）、SrCO3（99 %）Powder is according to stoichiometric proportion Ba0.95Sr0.05Zr0.01Ti0.99O3Weighed；
2nd, batch mixing：
The raw material that step one is weighed is put into ball milling in ball grinder, ball-milling medium is the mL of absolute ethyl alcohol 60 and zirconium oxide balls, Batch mixing is carried out with the h of ball mill ball milling 12, after ball milling, by ball milling gained slurry in insulation drying 1h at 120 DEG C；
3rd, pre-burning：
Powder after step 2 is dried is put into ceramic crucible, is warming up to 900 DEG C with the heating rate of 4 DEG C/min, and protect 2 h of temperature, then 1250 DEG C are warming up to the heating rate of 5 DEG C/min, and it is incubated 4h；
4th, granulate：
Powder is crushed through corase grind after step 3 is dried, and in transferring to ball grinder, and adds 45 mL absolute ethyl alcohols, ball milling 12 H, refines it, is placed in and 1 h. is dried in 100 DEG C of air dry oven, then adds 5wt.% polyvinyl alcohol and is fully ground 75 Granulated under Mpa pressure, be placed in agate mortar and crush, and ground, the material in mortar is constantly transferred to 60 in process of lapping On mesh sieve, it is crossed 60 mesh sieves and 140 mesh sieves, clout on 60 mesh sieves is transferred in mortar and continues to grind, 140 mesh sieve blankings are stayed Make bedding and padding, back and forth several times, until without clout on 60 mesh sieves；
5th, it is molded：
By on the mesh sieve of step 4 140 and 60 mesh sieve blanking powders are put into mould（φ=12 mm）Inner, under the pressure of 180MPa It is pressed into sequin type；
6th, plastic removal：
The sequin of step 6 is put into sintering furnace, 600 DEG C are warming up to the heating rate of 6 DEG C/min, insulation 2h enters Row dumping；
7th, sinter：
Disk after plastic removal in step 6 is put into ceramic crucible, with heating rate as 5 DEG C/min from room temperature to 1150-1250 DEG C, 60 min are incubated, temperature is risen to 1380 DEG C in 50 min afterwards, be incubated 15 min, then in 20 min 1400 DEG C are warming up to, 120 min are incubated, room temperature is cooled to stove, obtain Ba0.95Sr0.05Zr0.01Ti0.99O3；
8th, it is silver-colored
Ceramic sequin obtained in upper step is painted into silver paste in tow sides, after drying, 600 is heated in high temperature sintering furnace DEG C, and 30 min are incubated, obtain the ceramic sequin sample with silver electrode.
It should be appreciated that above-described embodiment is only explanation technology design of the invention and feature, this is familiar with its object is to allow The personage of item technology will appreciate that present disclosure and implement according to this that it is not intended to limit the scope of the present invention.It is all According to the equivalent change or modification that spirit of the invention is made, should all be included within the scope of the present invention.

Claims (5)

1. a kind of barium titanate-based lead-free piezoelectric ceramics, it is characterised in that：It is described ceramics component formula be（SrxBa1-x） （ZryTi1-y）O3, in formula, 0<X≤0.1,0<Y≤0.1, the atomicity percentage composition of Zr elements is 2at%-7at%.
2. a kind of method of the barium titanate-based lead-free piezoelectric ceramics prepared described in claim 1, it is characterised in that including following step Suddenly：
First, dispensing：
By raw material TiO2、ZrO2、BaCO3、SrCO3Powder is according to stoichiometric proportion（SrxBa1-x）（ZryTi1-y）O3Weighed, Wherein 0<X≤0.1,0< y ≤ 0.1 ；
2nd, batch mixing：
The raw material that step one is weighed is put into ball milling in ball grinder, ball-milling medium is absolute ethyl alcohol and zirconium oxide balls, wherein, ball Abrasive stick part is：Ratio of grinding media to material is 4：1：1, Ball-milling Time is 10-12h；After ball milling, by ball milling gained slurry at 80-120 DEG C Insulation drying 1h；
3rd, pre-burning：
Powder after step 2 is dried is put into ceramic crucible, and 800-900 is warming up to the heating rate of 3-5 DEG C/min DEG C, and 1-2 h are incubated, then 1150-1250 DEG C is warming up to the heating rate of 3-5 DEG C/min, and it is incubated 3-5h；
4th, granulate：
Powder grinds, sieves after step 3 is dried, and then addition 5wt.% polyvinyl alcohol is fully ground and is granulated, and takes On 140 mesh sieves and 60 mesh sieve blanking powders are standby；
5th, it is molded：
By on the mesh sieve of step 4 140 and 60 mesh sieve blanking powders are put into mould Inner, it is pressed under the pressure of 180-200MPa Sequin type；
6th, plastic removal：
The sequin of step 6 is put into sintering furnace, 550-650 DEG C, insulation are warming up to the heating rate of 4-6 DEG C/min 2-3h carries out dumping；
7th, sinter：
Disk after plastic removal in step 6 is put into ceramic crucible, with heating rate as 5 DEG C/min from room temperature to 1150-1250 DEG C, 60 min are incubated, temperature is risen to 1350-1380 DEG C in 40-50 min afterwards, be incubated 10-20 Min, then 1400 DEG C are warming up in 10-20 min, 120 min are incubated, it is cooled to room temperature with stove, obtain（SrxBa1-x）（ZryTi1-y） O3；
8th, it is silver-colored
Ceramic sequin obtained in upper step is painted into silver paste in tow sides, after drying, 600 is heated in high temperature sintering furnace DEG C, and 30 min are incubated, obtain the ceramic sequin sample with silver electrode.
3. the preparation method of barium titanate-based lead-free piezoelectric ceramics according to claim 2, it is characterised in that：Use planet Formula ball mill carries out wet-milling to material, and the rotating speed of planetary ball mill is 100-500 r/min；Preferably 300 r/min.
4. the preparation method of barium titanate-based lead-free piezoelectric ceramics according to claim 2, it is characterised in that：The step 5 The base substrate of middle compacting is disc-shaped structure, and blank diameter is 10-15mm；Preferably 12mm, thickness is 1-2mm.
5. a kind of electrode material, it is characterised in that：Including the barium titanate-based lead-free piezoelectric ceramics described in claim 1.
CN201611103908.0A 2016-12-05 2016-12-05 Barium titanate-based leadless piezoelectric ceramic and preparation method and application thereof Pending CN106699176A (en)

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CN107746206A (en) * 2017-10-31 2018-03-02 福州大学 A kind of High-energy-storage density dielectric material and preparation method thereof
CN107778004A (en) * 2017-11-15 2018-03-09 广东工业大学 A kind of zirconium barium-strontium titanate ceramic and its preparation method and application
CN111777411A (en) * 2020-06-22 2020-10-16 西安交通大学 Method for preparing donor-acceptor composite doped barium titanate-based ceramic by using semi-solution-solid phase sintering method
CN113735581A (en) * 2021-09-16 2021-12-03 湖南省美程陶瓷科技有限公司 Lead-free piezoelectric ceramic material and preparation method thereof

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JP2014172799A (en) * 2013-03-11 2014-09-22 Ricoh Co Ltd Piezoelectric material, manufacturing method of piezoelectric material, piezoelectric actuator, manufacturing method of piezoelectric actuator

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JP2014172799A (en) * 2013-03-11 2014-09-22 Ricoh Co Ltd Piezoelectric material, manufacturing method of piezoelectric material, piezoelectric actuator, manufacturing method of piezoelectric actuator
CN103265288A (en) * 2013-05-10 2013-08-28 伊犁师范学院 Large-dielectric-constant piezoelectric ceramic and preparation method thereof

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Publication number Priority date Publication date Assignee Title
CN107746206A (en) * 2017-10-31 2018-03-02 福州大学 A kind of High-energy-storage density dielectric material and preparation method thereof
CN107746206B (en) * 2017-10-31 2019-09-10 福州大学 A kind of High-energy-storage density dielectric material and preparation method thereof
CN107778004A (en) * 2017-11-15 2018-03-09 广东工业大学 A kind of zirconium barium-strontium titanate ceramic and its preparation method and application
CN107778004B (en) * 2017-11-15 2021-01-26 广东工业大学 Barium strontium zirconate titanate ceramic and preparation method and application thereof
CN111777411A (en) * 2020-06-22 2020-10-16 西安交通大学 Method for preparing donor-acceptor composite doped barium titanate-based ceramic by using semi-solution-solid phase sintering method
CN113735581A (en) * 2021-09-16 2021-12-03 湖南省美程陶瓷科技有限公司 Lead-free piezoelectric ceramic material and preparation method thereof
CN113735581B (en) * 2021-09-16 2022-07-15 湖南省美程陶瓷科技有限公司 Lead-free piezoelectric ceramic material and preparation method thereof

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Application publication date: 20170524