CN107162582A - Zinc oxide doped barium calcium zirconate titanate leadless piezoelectric ceramics - Google Patents

Zinc oxide doped barium calcium zirconate titanate leadless piezoelectric ceramics Download PDF

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CN107162582A
CN107162582A CN201710365064.5A CN201710365064A CN107162582A CN 107162582 A CN107162582 A CN 107162582A CN 201710365064 A CN201710365064 A CN 201710365064A CN 107162582 A CN107162582 A CN 107162582A
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zno
zirconate titanate
barium calcium
piezoelectric ceramics
calcium zirconate
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马卫兵
赵怀党
马民杰
郭靖栋
高骥风
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Tianjin University
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Tianjin University
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Abstract

The invention discloses a kind of ZnO doping barium calcium zirconate titanate leadless piezoelectric ceramics and preparation method thereof, its stoichiometric equation is (Ba0.85Ca0.15)(Zr0.10Ti0.90)O3Xmol%ZnO, wherein x=0.03~0.24.Pure phase (the Ba of currently available technology0.85Ca0.15)(Zr0.10Ti0.90)O3Piezoelectric property it is relatively low, d33For 300 or so.The present invention is based on barium calcium zirconate titanate piezoelectric ceramics, using traditional solid reaction process, adds ZnO to improve electric property, improves d33, prepare (the Ba with preferable combination property0.85Ca0.15)(Zr0.10Ti0.90)O3Xmol%ZnO piezoceramic materials, its sintering temperature is 1450 DEG C, during x=0.06, its εr=4928, d33=626pC/N.Piezoceramic material prepared by the present invention is mainly using fields such as piezoelectric transformer, piezoelectric generating unit, energy converter, sensor and receivers.Present invention process is simple, reduces cost, reduces pollution.

Description

Zinc oxide doped barium calcium zirconate titanate leadless piezoelectric ceramics
Technical field
The present invention is the ceramic composition on being characterized with composition, more particularly to (Ba0.85Ca0.15)(Zr0.10Ti0.90)O3 The leadless piezoelectric ceramics of system.
Background technology
Piezoelectric is to realize the class critical function material that electric energy and mechanical energy are mutually changed.Therefore piezoelectric is in machine The numerous areas such as tool, telecommunications, military affairs have a wide range of applications, and are the extremely important hi tech and new materials of a class.Its is main Using having：Piezoelectric transformer, piezoelectric ultrasonic transducer, piezo-electric relay, piezoelectric signal generator, standard signal source, wave filter Etc..
Electronic component almost spreads over each aspect of people's life now, but most of electronic components are leaded , the living environment given people causes severe contamination.Its reason is mainly at present in piezoelectric ceramics field, lead zirconate titanate base pottery It is all class material the most successful in terms of basic research and practicality that porcelain, which is, but be due to it is wherein leaded, prepare, using and All serious harm can be brought in discarded last handling process to the mankind and ecological environment.In this lead contamination increasingly serious situation Under, people become more urgent to the demand of " piezoelectric ceramics is unleaded ".In recent years, a series of national phases including China After having promulgated a series of decree, application of the lead-containing materials on electric power, electronic equipment is limited.Therefore, it is that lifting China is pressing The international competitiveness in electroceramics field, carrying out the innovative research of leadless piezoelectric ceramics has important strategic importance.Current nothing Lead piezoelectric ceramics system mainly has：Tungsten bronze structure leadless piezoelectric ceramics, bismuth laminated leadless piezoelectric ceramic, Ca-Ti ore type knot The types such as structure leadless piezoelectric ceramics.
(Ba0.85Ca0.15)(Zr0.10Ti0.90)O3It is that one kind has ABO3The perovskite structure ferroelectric of type, its feature bag Include：The excellent electric property such as higher dielectric constant, high tension performance, low-dielectric loss and positive temperature coefficient effect.Its crystal Structure has four kinds, be respectively cube to, Tetragonal, tripartite's phase and monoclinic phase.Current BCZT be widely used as energy converter, The field such as sensor and receiver.And it possesses excellent microwave property, and is used as multi layer substrate, ceramic capacitor, hair Optical device, antenna etc..Although BCZT ceramics are with excellent piezoelectric property, compared with lead base PZT piezoelectric ceramics, also have certain Deficiency, main piezoelectric property need to be improved, current this laboratory pure phase BCZT piezoelectric properties d33300 or so, by Some researchs in terms of formula, preparation technology and doping vario-property, to obtain excellent piezoelectric property, to realize it in piezoresistive material Application on material.
The content of the invention
The purpose of the present invention, is to solve (Ba0.85Ca0.15)(Zr0.10Ti0.90)O3Leadless piezoelectric ceramics piezoelectric property is relatively low Drawback, by adding ZnO raising electric properties, there is provided (the Ba that a kind of energy has preferable electric property0.85Ca0.15) (Zr0.10Ti0.90)O3System leadless piezoelectric ceramics.
The present invention is achieved by following technical solution.
A kind of ZnO doping barium calcium zirconate titanate leadless piezoelectric ceramics, its stoichiometric equation is (Ba0.85Ca0.15) (Zr0.10Ti0.90)O3- xmol%ZnO, wherein x=0.03~0.24；
The preparation method of the ZnO doping barium calcium zirconate titanate leadless piezoelectric ceramics, with following steps：
(1) dispensing
By raw materials of Ca CO3, BaCO3, TiO2 and ZrO2, based on (Ba0.85Ca0.15) (Zr0.10Ti0.90) O3 chemistry Amount ratio, and be put into after additional 0.03~0.24mol% ZnO mixing in ball grinder；Ball-milling medium is deionized water and oxidation Zirconium ball, ball：Material：The weight ratio of deionized water is 2：1：0.6；Compound is put into baking oven in 90 DEG C of drying again, is then placed in Ground in mortar, cross 40 mesh sieves；
(2) synthesize
The powder after being sieved in step (1) is put into crucible, be compacted, is capped, sealing, in 1150 DEG C in synthetic furnace Synthesis, is incubated 4h, naturally cools to room temperature, come out of the stove；
(3) secondary ball milling
The synthesis material of step (2) is put into ball mill grinding in ball grinder, then the material after ball milling is put into baking oven in 90 DEG C Drying, is then placed in grinding in mortar, crosses 60 mesh sieves；
(4) tabletting
Powder after step (3) is sieved, additional mass percent is granulated for 7wt.% polyvinyl alcohol water solution, Compression leg is homogenized, then is smashed to pieces, grinding sieving, and compressing is blank；
(5) dumping
The blank of step (4) is put into Muffle furnace, 650 DEG C are warming up to 5 DEG C/min speed, 1h is incubated, and in 200 DEG C and 350 DEG C of each insulation 1h, carry out organic matter exclusion；
(6) sinter
Put the blank after step (5) dumping into crucible addition bedding and padding to carry out burying burning, with 5 DEG C/min heating rate liter Temperature is incubated 4h, room temperature is naturally cooled to stove to 1350~1450 DEG C of sintering, and ZnO doping barium calcium zirconate titanate ceramics are made；
(7) electrode and surface treatment are applied
The ceramic upper and lower surfaces of ZnO doping barium calcium zirconate titanate piezoelectric that step (6) is obtained, which are polished to thickness, is 1mm, then coats elargol electrode using the mode of silk-screen printing in upper and lower surface, 735 is warming up to 7 DEG C/min heating rate DEG C silver ink firing, is incubated 15min.Cooling is put into silicone oil after taking out, and under the conditions of 25 DEG C, is polarized with DC electric field, is obtained ZnO doping Barium calcium zirconate titanate piezoelectric ceramics.
(8) piezoelectric property is tested
Piezoelectric ceramics after step (7) is polarized, in being stored at room temperature 24h, using Agilent, N5230C Network Analyzers, ZJ-3AN type quasistatics d33Measuring instrument tests its ε r, d33Performance.
Its stoichiometric equation is (Ba0.85Ca0.15)(Zr0.10Ti0.90)O3- xmol%ZnO, wherein x=0.06.
The Ball-milling Time of the step (1) is 6h, and drum's speed of rotation is 750 revs/min.
The Ball-milling Time of the step (3) is 12h, and drum's speed of rotation is 750 revs/min.
The compressing pressure of the step (4) is 200MPa.
The compressing blank of the step (4) is diameter 12mm, 1~1.5mm of thickness cylindric blank.
The sintering temperature of the step (6) is 1450 DEG C.
The Polarization field strength of the step (7) is 4500V/mm, and the polarization time is 25min.
Beneficial effects of the present invention, are with (Ba0.85Ca0.15)(Zr0.10Ti0.90)O3Based on piezoelectric ceramics, using addition ZnO improves piezoelectric coefficient d33Method, by be formulated with the adjustment and improvement of technique, to prepare with preferable combination property (Ba0.85Ca0.15)(Zr0.10Ti0.90)O3X=0.03~0.24 in-xmol%ZnO, formula, the present invention improves piezoelectric coefficient d33, A kind of preferable piezoelectric ceramics of combination property, wherein ε are obtainedr=4928, d33=626pc/N.
Brief description of the drawings
Fig. 1 is the dielectric constant collection of illustrative plates of the present invention；
Fig. 2 is the piezoelectric constant d of the present invention33Collection of illustrative plates.
Embodiment
The raw materials of Ca CO that the present invention is used3、BaCO3、TiO2、ZrO2And ZnO, be commercially available chemical pure raw material (purity >= 99%).
The preparation method of the present invention is as follows：
(1) dispensing
By raw materials of Ca CO3, BaCO3, TiO2 and ZrO2, based on (Ba0.85Ca0.15) (Zr0.10Ti0.90) O3 chemistry Amount ratio, and be put into after additional 0.03~0.24mol% ZnO mixing in ball grinder；Ball-milling medium is deionized water and oxidation Zirconium ball, ball：Material：The weight ratio of deionized water is 2：1：0.6；Compound is put into baking oven in 90 DEG C of drying again, is then placed in Ground in mortar, cross 40 mesh sieves；
(2) synthesize
The powder after being sieved in step (1) is put into crucible, be compacted, is capped, sealing, in 1150 DEG C in synthetic furnace Synthesis, is incubated 4h, naturally cools to room temperature, come out of the stove；
(3) secondary ball milling
The synthesis material of step (2) is put into ball mill grinding in ball grinder, then the material after ball milling is put into baking oven in 90 DEG C Drying, is then placed in grinding in mortar, crosses 60 mesh sieves；
(4) tabletting
Powder after step (3) is sieved, additional mass percent is granulated for 7wt.% polyvinyl alcohol water solution, Compression leg is homogenized, then is smashed to pieces, grinding sieving, and compressing is blank；
(5) dumping
The blank of step (4) is put into Muffle furnace, 650 DEG C are warming up to 5 DEG C/min speed, 1h is incubated, and in 200 DEG C and 350 DEG C of each insulation 1h, carry out organic matter exclusion；
(6) sinter
Put the blank after step (5) dumping into crucible addition bedding and padding to carry out burying burning, with 5 DEG C/min heating rate liter Temperature is incubated 4h, room temperature is naturally cooled to stove to 1350~1450 DEG C of sintering, and ZnO doping barium calcium zirconate titanate ceramics are made；
(7) electrode and surface treatment are applied
The ceramic upper and lower surfaces of ZnO doping barium calcium zirconate titanate piezoelectric that step (6) is obtained, which are polished to thickness, is 1mm, then coats elargol electrode using the mode of silk-screen printing in upper and lower surface, 735 is warming up to 7 DEG C/min heating rate DEG C silver ink firing, is incubated 15min.Cooling is put into silicone oil after taking out, and under the conditions of 25 DEG C, is polarized with DC electric field, is obtained ZnO doping Barium calcium zirconate titanate piezoelectric ceramics.
(8) piezoelectric property is tested
Piezoelectric ceramics after step (7) is polarized, in being stored at room temperature 24h, using Agilent, N5230C Network Analyzers, ZJ-3AN type quasistatics d33Measuring instrument tests its ε r, d33Performance.
Specific embodiment is as follows：
Comparative example x=0.00, sintering temperature is 1350 DEG C, and 1400 DEG C, 1450 DEG C, embodiment 1-1,1- is designated as respectively 2、1-3；
X=0.03, sintering temperature is 1350 DEG C, and 1400 DEG C, 1450 DEG C, embodiment 2-1,2-2,2-3 are designated as respectively；
X=0.06, sintering temperature is 1350 DEG C, and 1400 DEG C, 1450 DEG C, embodiment 3-1,3-2,3-3 are designated as respectively；
X=0.12, sintering temperature is 1350 DEG C, and 1400 DEG C, 1450 DEG C, embodiment 4-1,4-2,4-3 are designated as respectively；
X=0.24, sintering temperature is 1350 DEG C, and 1400 DEG C, 1450 DEG C, embodiment 5-1,5-2,5-3 are designated as respectively；
The piezoelectric property and dielectric constant test result of above-described embodiment are listed in table 1.
Table 1
Embodiment 3-3 is most preferred embodiment, as x=0.06, when sintering temperature is 1450 DEG C, εr=4928, d33= 626pc/N。
Fig. 1 shows that, when sintering temperature is 1350 DEG C, the dielectric constant of sample is substantially lower than other sintering temperatures, this Be due to that sintering temperature is relatively low, ceramics sample surface microstructure is small, grain growth not exclusively, defect and crack are more, compactness compared with Difference, stomata is more to be caused.When sintering temperature is increased to 1450 DEG C, each composition correspondence highest dielectric constant.In same sintering At a temperature of, with doping when increasing to x=0.06, the trend persistently increased is presented in its dielectric constant, but works as x=0.12 When, dielectric constant starts reduction, illustrates to become with the Diffuse phase transition behavior enhancing of doping ceramics sample, ceramic temperature stability It is good, increase dielectric constant.In addition, Zn (2+) enters (Ba0.85Ca0.15)(Zr0.10Ti0.90)O3Middle substitution Ti (4+) forms limited Solid solution, it may thus be appreciated that the solid solubility for allowing ZnO is x=0.06, works as x=0.12, and beyond solid solubility, dielectric constant declines.
Fig. 2 shows.It can be seen that for BCZT ceramics, with the rise of sintering temperature, the piezoelectricity of ceramics sample Property first increases to be reduced afterwards.When sintering temperature is 1450 DEG C, during doping x=0.06, ceramics sample has optimal piezoelectric property, Its piezoelectric coefficient d33=626pc/N, illustrates that the appropriate ZnO of doping is conducive to the improvement of the piezoelectric property of ceramics.This is produced to show As the reason for may be improved with appropriate doping ceramics compactness it is relevant.Research shows：The compactness of ceramics is better, its electricity Learn performance better.When doping is small, there is no dephasign generation in crystal, crystal grain is uniform, ceramic consistency increase.Thus piezoelectricity Performance is gradually stepped up in the range of to a certain degree；When the content is higher, ceramic grain growth has the trend of abnormal growth, internal There is stomata and the defect such as increase, the piezoelectric property that result in ceramics declines.
Piezoceramic material prepared by the present invention mainly applies piezoelectric transformer, piezoelectric generating unit, energy converter, sensing The field such as device and receiver.
The above-mentioned description to embodiment is easy for those skilled in the art and is understood that and using the present invention.It is ripe Know the personnel of art technology obviously can easily make various modifications to these embodiments, and general original described herein It ought to use in other embodiment without passing through performing creative labour.Therefore, the invention is not restricted to embodiment here, ability Field technique personnel are according to the announcement of the present invention, and the improvement made for the present invention and modification all should be in protection scope of the present invention Within.

Claims (8)

1. a kind of ZnO doping barium calcium zirconate titanate leadless piezoelectric ceramics, its stoichiometric equation is (Ba0.85Ca0.15)(Zr0.10Ti0.90) O3- xmol%ZnO, wherein x=0.03~0.24；
The preparation method of the ZnO doping barium calcium zirconate titanate leadless piezoelectric ceramics, with following steps：
(1) dispensing
By raw materials of Ca CO3、BaCO3、TiO2And ZrO2, by (Ba0.85Ca0.15)(Zr0.10Ti0.90)O3Stoichiometric proportion, and outside Plus 0.03~0.24mol% ZnO mixing after be put into ball grinder；Ball-milling medium is deionized water and zirconia ball, ball：Material： The weight ratio of deionized water is 2：1：0.6；Compound is put into baking oven in 90 DEG C of drying again, grinding in mortar is then placed in, Cross 40 mesh sieves；
(2) synthesize
The powder after being sieved in step (1) is put into crucible, is compacted, is capped, sealing is synthesized in synthetic furnace in 1150 DEG C, 4h is incubated, room temperature is naturally cooled to, comes out of the stove；
(3) secondary ball milling
The synthesis material of step (2) is put into ball mill grinding in ball grinder, then the material after ball milling is put into baking oven in 90 DEG C of drying, Grinding in mortar is then placed in, 60 mesh sieves are crossed；
(4) tabletting
Powder after step (3) is sieved, additional mass percent is granulated for 7wt.% polyvinyl alcohol water solution, compression leg Homogenizing, then smashed to pieces, grinding sieving, compressing is blank；
(5) dumping
The blank of step (4) is put into Muffle furnace, 650 DEG C are warming up to 5 DEG C/min speed, 1h is incubated, and in 200 DEG C and 350 DEG C of each insulation 1h, carry out organic matter exclusion；
(6) sinter
Put the blank after step (5) dumping into crucible addition bedding and padding to carry out burying burning, be warming up to 5 DEG C/min heating rate 1350~1450 DEG C of sintering, are incubated 4h, room temperature are naturally cooled to stove, and ZnO doping barium calcium zirconate titanate ceramics are made；
(7) electrode and surface treatment are applied
It is 1mm that the ceramic upper and lower surfaces of ZnO doping barium calcium zirconate titanate piezoelectric that step (6) is obtained, which are polished to thickness, so Elargol electrode is coated using the mode of silk-screen printing in upper and lower surface afterwards, 735 DEG C of burnings are warming up to 7 DEG C/min heating rate Silver, is incubated 15min.Cooling is put into silicone oil after taking out, and under the conditions of 25 DEG C, is polarized with DC electric field, is obtained ZnO doping zirconium titanium Sour barium calcium piezoelectric ceramics.
2. ZnO doping barium calcium zirconate titanate leadless piezoelectric ceramics according to claim 1, it is characterised in that its stoichiometric equation is (Ba0.85Ca0.15)(Zr0.10Ti0.90)O3- xmol%ZnO, wherein x=0.06.
3. ZnO doping barium calcium zirconate titanate leadless piezoelectric ceramics according to claim 1, it is characterised in that the ball of the step (1) Consume time as 6h, drum's speed of rotation is 750 revs/min.
4. ZnO doping barium calcium zirconate titanate leadless piezoelectric ceramics according to claim 1, it is characterised in that the ball of the step (3) Consume time as 12h, drum's speed of rotation is 750 revs/min.
5. ZnO doping barium calcium zirconate titanate leadless piezoelectric ceramics according to claim 1, it is characterised in that step (4) compacting The pressure of shaping is 200MPa.
6. ZnO doping barium calcium zirconate titanate leadless piezoelectric ceramics according to claim 1, it is characterised in that step (4) compacting The blank of shaping is diameter 12mm, 1~1.5mm of thickness cylindric blank.
7. ZnO doping barium calcium zirconate titanate leadless piezoelectric ceramics according to claim 1, it is characterised in that the burning of the step (6) Junction temperature is 1450 DEG C.
8. ZnO doping barium calcium zirconate titanate leadless piezoelectric ceramics according to claim 1, it is characterised in that the pole of the step (7) Change field strength is 4500V/mm, and the polarization time is 25min.
CN201710365064.5A 2017-05-22 2017-05-22 Zinc oxide doped barium calcium zirconate titanate leadless piezoelectric ceramics Pending CN107162582A (en)

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CN116283270A (en) * 2023-03-31 2023-06-23 中山大学 ZnO-BaTiO 3 Preparation method of composite target material

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Application publication date: 20170915