CN108083797A - High mechanical quality factor barium calcium zirconate titanate base ceramics and its low-temperature melt producing method - Google Patents

High mechanical quality factor barium calcium zirconate titanate base ceramics and its low-temperature melt producing method Download PDF

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CN108083797A
CN108083797A CN201810068621.1A CN201810068621A CN108083797A CN 108083797 A CN108083797 A CN 108083797A CN 201810068621 A CN201810068621 A CN 201810068621A CN 108083797 A CN108083797 A CN 108083797A
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陈小明
李国荣
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Guizhou Institute of Technology
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Abstract

The invention discloses a kind of high mechanical quality factor barium calcium zirconate titanate base ceramics, and disclose the preparation method and purposes of this kind of leadless piezoelectric ceramics.Its raw material components and mass percent are:Its raw material components and mass percent are:（Ba0.85Ca0.15）（Ti0.9Zr0.1）O3‑x wt%Li2CO3, 0<X ￡ 1.0, wherein Li2CO3For fluxing agent, sintering temperature is 1,300 1450oC keeps the temperature 2h, wherein Li2CO3For fluxing agent.Sintering temperature of the present invention is low, has high tension performance, higher mechanical quality factor, the loss of low room temperature dielectric.Good combination property can meet the application in the electronic devices such as resonator.

Description

High mechanical quality factor barium calcium zirconate titanate base ceramics and its low-temperature melt producing method
Technical field
Preparation and synthesis technical field the invention belongs to leadless piezoelectric ceramics, and in particular to a kind of high mechanical quality factor Barium calcium zirconate titanate base ceramics and its low-temperature melt producing method.
Background technology
Piezoelectric ceramics has a wide range of applications in electronic field, but is mostly leaded.And leadless piezoelectric ceramics is because having The characteristics of environmentally friendly and the extensive concern for causing people.( Takenaka T., Nagata H.. Current status and prospects of lead-free piezoelectric ceramics [J]. J Eur Ceram Soc, 2005, 25 2693-700, Panda. Review: environmental friendly lead-free piezoelectric materials [J]. J Mater Sci, 2009, 44:5049-62.) BaTiO3 base ceramics obtain Related scholar's numerous studies, and the ceramic systems of preferable piezoelectric property are obtained, e.g., BaTiO3-KNbO3 Wada Satoshi., Nitta M., Kumada N., Tanaka D., Furukawa M., Ohno S., Moriyoshi C., Kuroiwa Y. Preparation of barium titanate-potassium niobate solid solution system ceramics and their piezoelectric properties [J]. Japanese Journal Of Applied Physics, 2008, 47: 7678-84.).It is reported that the piezoelectric property of (Ba, Ca) (Ti, Zr) O3 ceramics It can compare favourably with lead base ceramics Pb (Ti, Zr) O3.Due to the presence of polycrystalline state phase transformation at room temperature, its piezoelectric constant is reachable 650pC/N( Liu Wenfeng, Ren Xiaobing. Large Piezoelectric Effect in Pb-Free Ceramics [J]. Phys Rev Lett, 2009, 103: 257602.).Although it shows good piezoelectric property, But required technological temperature is high：The calcined temperature of powder should be at 1300 DEG C or so, and ceramic sintering temperature should be controlled very narrow Temperature range（1520- 1550℃）.( Wang Pan , Li Yong Xiang , Lu Yi Qing. Enhanced piezoelectric properties of (Ba0.85 Ca0.15 )(Ti0.9 Zr0.1 )O3 lead-free ceramics by optimizing calcination and sintering temperature [J]. J Eur Ceram Soc, 2011, 31:2005-12.), in addition, it has low mechanical quality factor（<100）The shortcomings of, limit its work Industry metaplasia is produced and application.
The Chinese patent literature of publication number CN 102910905A (Application No. 201210409868.8) discloses one Low sintering barium calcium zirconate titanate based leadless piezoelectric ceramics of kind and preparation method thereof.Its raw material components and molar percentage are (1- x)(Ba0.865Ca0.135)(Ti0.89Zr0.11)O3- xCuO, wherein 0 ＜ x ＜ 0.1；Sintering temperature is 1350~1450 DEG C, heat preservation 2h.But technology disclosed in above patent document only improves (Ba, Ca) (Ti, Zr) O3The piezoelectric constant of piezoelectric ceramics with Sintering temperature (CN 102910905A) is reduced, and is not directed to the mechanical quality factor of piezoelectric ceramics.Mechanical quality factor is being pressed It plays a key effect in electroceramics practical application, when piezoelectric ceramics has relatively low mechanical quality factor, mechanical loss is big, uses Longevity, thus can not be used widely.Currently, each state all put into substantial amounts of energy improve (Ba, Ca) (Ti, Zr)O3Base ceramic performance, to reach application request, but can apply still seldom, therefore, research and develop new (Ba, Ca) (Ti, Zr)O3Based leadless piezoelectric ceramics are imperative.
The content of the invention
The present invention provides a kind of high mechanical quality factor barium calcium zirconate titanate base to solve shortcoming of the prior art Ceramics and its low-temperature melt producing method；The present invention according to different sintering temperatures, can obtain the corresponding material of high mechanical quality factor Material formula carrys out making devices, so as to be applied in the electronic devices such as vibrator, piezoelectric ceramics resonator.
In order to solve the above technical problems, the present invention adopts the following technical scheme that：High mechanical quality factor barium calcium zirconate titanate base Ceramics, raw material components and mass percent are:（Ba0.85Ca0.15）（Ti0.9Zr0.1）O3-x wt % Li2CO3,, Wherein Li2CO3For fluxing agent.
High mechanical quality factor barium calcium zirconate titanate base ceramic low-temp sintering preparation method, the method are synthesis in solid state Method, including step in detail below：
A. according to the stoichiometric ratio of raw material components, using purity as 99% BaCO3, purity be 99.48% TiO2, purity 99 The CaCO of %3With the ZrO that purity is 99.84%2It for starting material, is weighed respectively, BaCO3、TiO2、CaCO3And ZrO2；'s Mass ratio is 75.9919：32.4080：6.8017：5.5353；
B. the load weighted raw mixtures of step a are put into ball grinder and carry out ball milling, be sufficiently mixed 6h, use ball-milling medium For absolute ethyl alcohol and zirconia ball, the mass ratio of raw material, absolute ethyl alcohol and zirconia ball is 1:1 :1.5, after a ball milling, Mixture is moved to 80oIt is dried in the convection oven of C, is dry, then mixture is put into mortar and is ground, crossing 40 mesh sieves；
C. the step b raw material to sieve are put in and are put into mold, manipulation forcing press applies 7Mpa pressure, pressurize 30s, then moves into crucible In, crucible cover is closed, is put into chamber type electric resistance furnace, according to the heating rate of 5 DEG C/min, the temperature of crucible is made to rise to 1200 oC, 2h pre-synthesis is kept, resistance furnace is then turned off, with resistance furnace cooled to room temperature；
D. the pre-synthesis object of step c, it is placed again into mortar and grinds, crosses 40 mesh sieves；According to the stoichiometry of raw material components Than adding in Li2CO3, ball-milling medium is used as absolute ethyl alcohol and zirconia ball, pre-synthesis object, Li2CO3, absolute ethyl alcohol and oxygen The mass ratio for changing zirconium ball is 100：71：Mixture after secondary ball milling, is moved to 80 by 150, abundant ball milling mixing 6hoThe air blast of C is dried It is dried in case, is dry, placed into mortar and grind, crossing 40 mesh sieves；
E. the powder after step d drying and screenings, binding agent PVA aqueous solutions are added in, granulation obtains the particle of good flowing properties； Particle after granulation is put in and is put into mold, manipulation forcing press applies 7Mpa pressure, pressurize 30s, then moves into mortar and grind, mistake 40 mesh sieves；
F. step e be granulated sieving after powder be put into compression mold, manipulation forcing press under 1-2Mpa pressure dry-pressing into Type carries out plastic removal after obtaining green sheet, and the plasticizer contained in green sheet or adhesive are discharged；
G. the green sheet of step f is placed on crucible plate, and is embedded to raw material powder, it is then raw convenient for forming corresponding atmosphere during sintering Crucible is buckled in blank, then crucible plate and crucible are put into chamber type electric resistance furnace, with the heating rate of 5 DEG C/min, makes temperature 1200-1450 DEG C is risen to, 2h is kept the temperature, is sintered, is then turned off resistance furnace, with resistance furnace cooled to room temperature, prepare Barium calcium zirconate titanate based leadless piezoelectric ceramics；
H. the piezoelectric ceramic piece of step g sintering is carried out the two-sided thickness that is polishing to as 0.8mm, using silk-screen printing technique, made pottery Tile is two-sided to coat silver paste, forms silver electrode；At this point, piezoelectric ceramic piece is put into chamber type electric resistance furnace, with 5 DEG C/min speed Rate is warming up to 650oC keeps the temperature 20min, reaches room temperature with stove natural cooling, takes out piezoelectric ceramic piece, retain upper and lower surface Silver electrode grinds off side silver electrode；
I. electrical performance testing is carried out to the piezoelectric ceramic piece in step h.
Drum's speed of rotation in the step b and d is 350 revs/min, and every 30 minutes, the ball milling of ball mill turned to By clockwise and counterclockwise alternately.
The mass fraction for the binding agent PVA aqueous solutions that the step e is added is 5%.
A diameter of Φ 12mm of compression mold, dry-pressing formed under 1-2Mpa pressure in the step f., obtains thickness 1.2 ~1.5mm, a diameter of 12mm, cylindrical green sheet.
Sintering temperature in the step g is 1400-1450 DEG C.
The test of the step i is specially：The piezoelectric ceramic piece for coating silver electrode is placed in 20-30 DEG C of silicone oil and is applied The DC electric field of 4~5kV/mm, polarize 20~30min, the associated electrical performance of sample again after diel to be placed.
Using above-mentioned technical proposal, the barium calcium zirconate titanate base leadless piezoelectricity pottery of high mechanical quality factor provided by the invention Porcelain, the piezo ceramic element characteristic as obtained by aforementioned preparation process flow are as follows：
1st, such barium calcium zirconate titanate based leadless piezoelectric ceramics have relatively high mechanical quality factor：Q m =130-248。
2nd, such barium calcium zirconate titanate based leadless piezoelectric ceramics have relatively high piezoelectric property：d 33 =165-463 pC/N,k p =0.13 -0.49
3rd, such barium calcium zirconate titanate based leadless piezoelectric ceramics have low dielectric loss=0.009-0.018, high dielectric are normal Number= 1160 - 4864 。
4th, the present invention reduces sintering temperature, material shows higher mechanical quality factor by adding in fluxing agentQ m （238）, low dielectric loss（0.009）, there is very big application to dive in the electronic devices such as vibrator, piezoelectric ceramics resonator Power.
In conclusion the sintering temperature of the present invention is low, there is high tension performance, higher mechanical quality factor, low room Warm dielectric loss.Good combination property can meet the application in the electronic devices such as resonator.
Description of the drawings
Fig. 1 is 1 gained Ba of the embodiment of the present invention0.85Ca0.15Ti0.9Zr0.1O3-0.7wt % Li2CO3XRD crystalline phase figures；
Fig. 2 is 1 gained Ba of the embodiment of the present invention0.85Ca0.15Ti0.9Zr0.1O3-0.5wt % Li2CO3Dielectric constant with temperature Changing rule schematic diagram；
Fig. 3 is 1 gained Ba of the embodiment of the present invention0.85Ca0.15Ti0.9Zr0.1O3-xwt % Li2CO3, the machine under different sintering temperatures Tool quality factorQ m Variation with temperature rule schematic diagram.
Specific embodiment
The high mechanical quality factor barium calcium zirconate titanate base ceramics and its low-temperature melt producing method of the present invention, including following step Suddenly,
The features of the present invention is further expressed below by embodiment, embodiment is only to illustrate goal of the invention, but is not intended as The foundation limited the present invention.
Embodiment 1：According to above-mentioned traditional ceramics preparation process, fine and close ceramic body is can obtain, specifically, with BaCO3 (99%), TiO2(99.48%), CaCO3(99%), and ZrO2(99.84%) it is starting material, by component stoichiometry ratio It is weighed, BaCO3、TiO2、CaCO3And ZrO2；Mass ratio be 75.9919：32.4080：6.8017：5.5353.By original Expect mixture ball milling 6-7h, after being sufficiently mixed, crushing, pre-synthesis is carried out under 1200 DEG C/2h；Ceramic powders after synthesis are abundant It grinds and adds in x wt% Li2CO3(99.31%) (x=0.1,0.3,0.5,0.7,1.0), it is after drying plus suitable after secondary ball milling The binding agent PVA of amount, granulation obtains the particle of good flowing properties, dry-pressing formed under a certain pressure, and acquisition thickness 1.2~ The green sheet of 1.5mm, a diameter of 12mm, plastic removal, then through being sintered 2 h at a temperature of 1300-1400 DEG C, be as above formulated Piezoelectric ceramic piece.The electric property of last test piezoelectric ceramic piece is applied after piezoelectric ceramics on piece silver electrode in 30 DEG C of silicone oil The DC electric field of 4~5kV/mm is added to polarize 20~30min, the associated electrical performance of diel to be placed sample again.It is led Performance parameter is wanted to be listed in table 1.It can be seen that the sample formed near x=0. 5 has optimal comprehensive performance.
1 Ba of table0.85Ca0.15Ti0.9Zr0.1O3-xwt % Li2CO3The typical performance of sample（1400 DEG C/2h of sintering temperature）
Fig. 1 is gained piezoelectric ceramics Ba0.85Ca0.15Ti0.9Zr0.1O3-0.7wt % Li2CO3XRD crystalline phase figures, it is seen then that ceramics With the single perovskite structure of typical case.Fig. 2 is gained piezoelectric ceramics Ba0.85Ca0.15Ti0.9Zr0.1O3-0.5wt % Li2CO3's Dielectric constantWith temperatureTChanging rule.As it can be seen that within the temperature range of testing, the ceramic relative dielectric constantε rWith Temperature and increase, and in Curie temperatureT cReach maximum, this and BaTiO3Ceramics are similar.The tan of ceramicsδ- T curve-100- In 210 DEG C of temperature ranges, there is relatively low dielectric loss（<0.04）.Fig. 3 is gained piezoelectric ceramics Ba0.85Ca0.15Ti0.9Zr0.1O3-xwt % Li2CO3, the mechanical quality factor under different sintering temperaturesQ m Variation with temperature is advised Restrain schematic diagram.When sintering temperature is 1400-1450 DEG C, during x=0.5-0.7, mechanical quality factorQ m Obtain maximum.
Embodiment 2. is with BaCO3 (99%), TiO2(99.48%), CaCO3(99%), and ZrO2(99.84%) it is Starting material is weighed, BaCO by component stoichiometry ratio3、TiO2、CaCO3And ZrO2；Mass ratio be 75.9919： 32.4080：6.8017：5.5353.By raw mixture ball milling 6-7h, after being sufficiently mixed, crushing, carried out under 1200 DEG C/2h Pre-synthesis；Ceramic powders after synthesis are fully ground and add in 0.7wt% Li2CO3(99.31%) after, sintering temperature 1450 DEG C, other technical process are identical with embodiment 1.Its Specifeca tion speeification is listed in table 2.It can be seen that near x=0. 7 It is 248 that the sample of composition, which has higher mechanical quality factor,.
2 Ba of table0.85Ca0.15Ti0.9Zr0.1O3-0.7wt % Li2CO3The typical performance of sample
The present embodiment is every according to the invention not to the limitation of works in any form such as shape, material, the structures of the present invention Any simple modification, equivalent change and modification that technical spirit makees above example, belongs to technical solution of the present invention Protection domain.

Claims (7)

1. high mechanical quality factor barium calcium zirconate titanate base is ceramic, it is characterised in that：Its raw material components and mass percent are: （Ba0.85Ca0.15）（Ti0.9Zr0.1）O3-x wt % Li2CO3, 0<X ￡ 1.0, wherein Li2CO3For fluxing agent.
2. high mechanical quality factor barium calcium zirconate titanate base ceramic low-temp sintering preparation method as described in claim 1 is used, It is characterized in that：The method is solid-phase synthesis, including step in detail below：
A. according to the stoichiometric ratio of raw material components, using purity as 99% BaCO3, purity be 99.48% TiO2, purity 99 The CaCO of %3With the ZrO that purity is 99.84%2It for starting material, is weighed respectively, BaCO3、TiO2、CaCO3And ZrO2；'s Mass ratio is 75.9919：32.4080：6.8017：5.5353；
B. the load weighted raw mixtures of step a are put into ball grinder and carry out ball milling, be sufficiently mixed 6h, use ball-milling medium For absolute ethyl alcohol and zirconia ball, the mass ratio of raw material, absolute ethyl alcohol and zirconia ball is 1:1 :1.5, after a ball milling, Mixture is moved to 80oIt is dried in the convection oven of C, is dry, then mixture is put into mortar and is ground, crossing 40 mesh sieves；
C. the step b raw material to sieve are put in and are put into mold, manipulation forcing press applies 7Mpa pressure, pressurize 30s, then moves into crucible In, crucible cover is closed, is put into chamber type electric resistance furnace, according to the heating rate of 5 DEG C/min, the temperature of crucible is made to rise to 1200 oC, 2h pre-synthesis is kept, resistance furnace is then turned off, with resistance furnace cooled to room temperature；
D. the pre-synthesis object of step c, it is placed again into mortar and grinds, crosses 40 mesh sieves；According to the stoichiometry of raw material components Than adding in Li2CO3, ball-milling medium is used as absolute ethyl alcohol and zirconia ball, pre-synthesis object, Li2CO3, absolute ethyl alcohol and oxygen The mass ratio for changing zirconium ball is 100：71：Mixture after secondary ball milling, is moved to 80 by 150, abundant ball milling mixing 6hoThe air blast of C is dried It is dried in case, is dry, placed into mortar and grind, crossing 40 mesh sieves；
E. the powder after step d drying and screenings, binding agent PVA aqueous solutions are added in, granulation obtains the particle of good flowing properties； Particle after granulation is put in and is put into mold, manipulation forcing press applies 7Mpa pressure, pressurize 30s, then moves into mortar and grind, mistake 40 mesh sieves；
F. step e be granulated sieving after powder be put into compression mold, manipulation forcing press under 1-2Mpa pressure dry-pressing into Type carries out plastic removal after obtaining green sheet, and the plasticizer contained in green sheet or adhesive are discharged；
G. the green sheet of step f is placed on crucible plate, and is embedded to raw material powder, it is then raw convenient for forming corresponding atmosphere during sintering Crucible is buckled in blank, then crucible plate and crucible are put into chamber type electric resistance furnace, with the heating rate of 5 DEG C/min, makes temperature 1200-1450 DEG C is risen to, 2h is kept the temperature, is sintered, is then turned off resistance furnace, with resistance furnace cooled to room temperature, prepare Barium calcium zirconate titanate based leadless piezoelectric ceramics；
H. the piezoelectric ceramic piece of step g sintering is carried out the two-sided thickness that is polishing to as 0.8mm, using silk-screen printing technique, made pottery Tile is two-sided to coat silver paste, forms silver electrode；At this point, piezoelectric ceramic piece is put into chamber type electric resistance furnace, with 5 DEG C/min speed Rate is warming up to 650oC keeps the temperature 20min, reaches room temperature with stove natural cooling, takes out piezoelectric ceramic piece, retain upper and lower surface Silver electrode grinds off side silver electrode；
I. electrical performance testing is carried out to the piezoelectric ceramic piece in step h.
3. low-temperature melt producing method according to claim 2, it is characterised in that：Ball milling in the step b and d Machine rotating speed is 350 revs/min, and every 30 minutes, the ball milling of ball mill, which turns to, to be pressed clockwise and counterclockwise alternately.
4. low-temperature melt producing method according to claim 2, it is characterised in that：The binding agent that the step e is added The mass fraction of PVA aqueous solutions is 5%.
5. low-temperature melt producing method according to claim 2, it is characterised in that：Compression mold is straight in the step f. Footpath is Φ 12mm, dry-pressing formed under 1-2Mpa pressure, obtains 1.2~1.5mm of thickness, a diameter of 12mm, cylindrical green compact Piece.
6. low-temperature melt producing method according to claim 2, it is characterised in that：Sintering temperature in the step g is 1400-1450℃。
7. low-temperature melt producing method according to claim 2, it is characterised in that：The test of the step i is specially：It will Coat silver electrode piezoelectric ceramic piece be placed in 20-30 DEG C of silicone oil apply 4~5kV/mm DC electric field, polarization 20~ 30min, the associated electrical performance of sample again after diel to be placed.
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CN109824356A (en) * 2019-03-19 2019-05-31 武汉理工大学 A kind of barium phthalate base high performance piezoelectric ceramic material and preparation method thereof
CN110739529A (en) * 2019-09-30 2020-01-31 无锡惠虹电子有限公司 novel ceramic antennas and preparation method thereof
CN111153696A (en) * 2020-01-06 2020-05-15 天津大学 Low-temperature sintered barium calcium zirconate titanate-based lead-free high-energy-storage-efficiency ceramic material
CN111333413A (en) * 2020-03-06 2020-06-26 中国科学院上海硅酸盐研究所 Bismuth ferrite-lead titanate-barium titano-stannate ternary system high-temperature piezoelectric ceramic material and preparation method thereof
CN111333413B (en) * 2020-03-06 2021-08-06 中国科学院上海硅酸盐研究所 Bismuth ferrite-lead titanate-barium titano-stannate ternary system high-temperature piezoelectric ceramic material and preparation method thereof
CN111499382A (en) * 2020-04-28 2020-08-07 天津大学 High-temperature-stability double-layer energy storage ceramic and preparation method thereof
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