CN113979747A - Modified lead zirconate titanate piezoelectric ceramic with additional bismuth antimonate and preparation method thereof - Google Patents

Modified lead zirconate titanate piezoelectric ceramic with additional bismuth antimonate and preparation method thereof Download PDF

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CN113979747A
CN113979747A CN202111369115.4A CN202111369115A CN113979747A CN 113979747 A CN113979747 A CN 113979747A CN 202111369115 A CN202111369115 A CN 202111369115A CN 113979747 A CN113979747 A CN 113979747A
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lead zirconate
zirconate titanate
piezoelectric ceramic
modified lead
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丁忆
余洋
王海圣
许静玲
翁新全
柯银鸿
刘瑞林
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Xiamen Niell Electronics Co ltd
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Abstract

The invention discloses a modified lead zirconate titanate piezoelectric ceramic with additional bismuth antimonate and a preparation method thereof, relating to the technical field of piezoelectric ceramics3And a small amount of CeO2And Sm2O3Carrying out doping modification, wherein the formula is as follows: (1-u) Pb1‑x‑ySrxLay(ZrzTi1‑z)O3‑uBiSbO3‑vwt％CeO2‑hwt％Sm2O3. Wherein: x is more than or equal to 0 and less than or equal to 0.5, y is more than or equal to 0 and less than or equal to 0.5, z is more than or equal to 0.3 and less than or equal to 0.7, u is more than or equal to 0 and less than or equal to 0.3, v is more than or equal to 0 and less than or equal to 0.3, and h is more than or equal to 0 and less than or equal to 0.3. After the technical scheme is adopted, the inventionThe dielectric loss of the PZT ceramic can be reduced while the high-voltage performance is maintained, and the generation of noise in the signal output process is reduced.

Description

Modified lead zirconate titanate piezoelectric ceramic with additional bismuth antimonate and preparation method thereof
Technical Field
The invention relates to the technical field of piezoelectric ceramics, in particular to modified lead zirconate titanate piezoelectric ceramics with additional bismuth antimonate and a preparation method thereof.
Background
With the rapid advance of scientific technology, the research on the piezoelectric ceramic material is more and more intensive, and the corresponding application scenes and fields are more and more extensive. Piezoelectric ceramics are materials which can realize interconversion between electric energy and mechanical energy. Among the most widely commercialized ceramics are the lead zirconate titanate (PZT) series piezoelectric ceramics. Researchers have developed various types of PZT ceramics for different application scenarios and usage purposes. Wherein the high piezoelectric property and the low Curie temperature are soft PZT which is a PZT-5 system; the piezoelectric performance of high quality factor, low dielectric loss and relatively low piezoelectric performance is called hard ceramic and is a PZT-4 system; it is often difficult to combine high piezoelectric performance with low dielectric loss.
In view of the above, the present invention is conceived based on the deficiencies caused by the above-mentioned perfection, and the present invention is designed by actively researching and improving the present invention.
Disclosure of Invention
The invention aims to provide a modified lead zirconate titanate piezoelectric ceramic with additional bismuth antimonate and a preparation method thereof, wherein the modified lead zirconate titanate piezoelectric ceramic can maintain high-voltage performance, reduce dielectric loss of PZT ceramic and reduce noise in the signal output process.
In order to achieve the purpose, the invention adopts the following technical scheme:
a modified lead zirconate titanate piezoelectric ceramic with additional bismuth antimonate is prepared by co-doping Sr/La at A position of PZT ceramic and additionally adding BiSbO3And a small amount of CeO2And Sm2O3Carrying out doping modification, wherein the formula is as follows:
(1-u)Pb1-x-ySrxLay(ZrzTi1-z)O3-uBiSbO3-vwt％CeO2-hwt％Sm2O3
wherein: x is more than or equal to 0 and less than or equal to 0.5, y is more than or equal to 0 and less than or equal to 0.5, z is more than or equal to 0.3 and less than or equal to 0.7, u is more than or equal to 0 and less than or equal to 0.3, v is more than or equal to 0 and less than or equal to 0.3, and h is more than or equal to 0 and less than or equal to 0.3.
The invention also aims to provide a preparation method of the modified lead zirconate titanate piezoelectric ceramic with additional bismuth antimonate, which comprises the following steps:
the method comprises the following steps: with SrCO3、La2O3、ZrO2、TiO2、Sb2O3、Bi2O3、Pb 304、CeO2、Sm2O3Weighing Pb, Sr, La, Zr, Ti, Sb, Bi, Ce and Sm in the formula according to the stoichiometric ratio of Pb, Sr, La, Zr, Ti, Sb, Bi, Ce and Sm, and mixing in an alcohol solvent;
step two: rolling and grinding by using zirconium balls, drying alcohol, and pre-burning after drying to obtain pre-burned powder;
step three: performing secondary ball milling on the presintered powder, and then performing secondary drying to obtain secondarily dried powder;
step four: adding PVA solution into the secondarily dried powder, fully grinding the powder, and pressing the powder into small wafers;
step five: performing glue discharging treatment on the pressed small round piece, and sintering the small round piece after glue discharging to obtain a ceramic piece;
step six: covering silver paste on two ends of the ceramic chip, then carrying out silver burning treatment, then carrying out polarization treatment on the ceramic chip after silver burning, obtaining the modified lead zirconate titanate piezoelectric ceramic with additional bismuth antimonate after polarization is finished, and carrying out testing after standing for a period of time.
Further, in the second step, the time for rolling and grinding the zirconium balls is 24 hours.
Further, in the second step, the pre-sintering temperature is 900 ℃, and the heat preservation time is 2 hours.
Further, in the third step, the time of secondary ball milling is 13 hours.
Further, in the fourth step, the mass ratio of the PVA solution is 8%, and the powder after the secondary drying is pressed into small wafers in 1.5 PMa.
Further, in the fifth step, the temperature of the glue discharging treatment is 750 ℃, the heat preservation time is 2 hours, the sintering temperature is 1200 ℃, and the heat preservation time is 2 hours.
Further, in the sixth step, the silver burning temperature is 650 ℃, the polarization temperature is 140 ℃, the polarization voltage is 4kV/mm, the polarization heat preservation time is 30min, and the standing time is 24 h.
After the technical scheme is adopted, the piezoelectric ceramic prepared according to the formula shows excellent comprehensive electrical properties, a sample prepared according to the formula can obtain high piezoelectric properties and keep higher distance temperature, so that the piezoelectric ceramic material has high electromechanical conversion capacity and a wider applicable range, and meanwhile, the lower dielectric loss and the dielectric constant are favorable for reducing the output of noise.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 shows a piezoelectric ceramic of example 1 of the present invention having a 2. theta. angle of 20 to 60OXRD diffractogram of.
FIG. 2 is a dielectric thermogram of example 1.
Detailed Description
In order to further explain the technical solution of the present invention, the present invention is explained in detail by the following specific examples.
In the description of the present invention, it is to be understood that the terms "center", "longitudinal", "lateral", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", and the like, indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are used merely for convenience in describing the present invention and for simplicity in description, and do not indicate or imply that the devices or elements referred to must have a particular orientation, be constructed in a particular orientation, and be operated, and thus, are not to be construed as limiting the present invention. In the description of the present invention, "a plurality" means two or more unless otherwise specified.
A modified lead zirconate titanate piezoelectric ceramic with additional bismuth antimonate is prepared by co-doping Sr/La at A position of PZT ceramic and additionally adding BiSbO3And a small amount of CeO2And Sm2O3Carrying out doping modification, wherein the formula is as follows:
(1-u)Pb1-x-ySrxLay(ZrzTi1-z)O3-uBiSbO3-vwt％CeO2-hwt％Sm2O3
wherein: x is more than or equal to 0 and less than or equal to 0.5, y is more than or equal to 0 and less than or equal to 0.5, z is more than or equal to 0.3 and less than or equal to 0.7, u is more than or equal to 0 and less than or equal to 0.3, v is more than or equal to 0 and less than or equal to 0.3, and h is more than or equal to 0 and less than or equal to 0.3.
The following are some specific examples of the modified lead zirconate titanate piezoelectric ceramic component with bismuth antimonate added in the invention:
example 1
The molecular formula of the preparation formula is as follows:
0.99Pb0.97Sr0.02La0.01(Zr0.53Ti0.47)O3-0.01BiSbO3-0.1％wtCeO2-0.1％wtSm2O3the modified lead zirconate titanate piezoelectric ceramic added with the bismuth antimonate.
Wherein: u is 0.01, x is 0.02, y is 0.01, z is 0.53, v is 0.1, and h is 0.1.
The preparation method comprises the following steps:
the method comprises the following steps: with SrCO3、La2O3、ZrO2、TiO2、Sb2O3、Bi2O3、Pb 304、CeO2、Sm2O3Weighing Pb, Sr, La, Zr, Ti, Sb, Bi, Ce and Sm in the formula according to the stoichiometric ratio of Pb, Sr, La, Zr, Ti, Sb, Bi, Ce and Sm, and mixing in an alcohol solvent;
step two: grinding with zirconium ball for 24 hr, drying to obtain alcohol extract, and pre-sintering at 900 deg.C for 2 hr to obtain pre-sintered powder;
step three: performing secondary ball milling on the presintered powder in a ball milling tank, and performing secondary drying after performing roller milling for 13h to obtain dried powder;
step four: adding a PVA solution with the mass ratio of 8% into the secondarily dried powder, fully grinding until the glue is uniformly dispersed, and pressing into a small wafer under the pressure of 1.5 MPa;
step five: keeping the pressed small wafer at 750 ℃ for 2h for carrying out glue removing treatment, and keeping the sample at 1200 ℃ for 2h for sintering to obtain a ceramic wafer;
step six: covering silver paste on two ends of the ceramic wafer, then carrying out silver firing treatment at 650 ℃, then placing the ceramic wafer in an environment at 140 ℃, applying a 4kV/mm electric field, preserving heat for 30min, carrying out polarization treatment, obtaining the modified lead zirconate titanate piezoelectric ceramic with the additional bismuth antimonate after the polarization is finished, and standing for 24h to test corresponding electrical properties.
The main parameters are d33 ═ 544pC/N, TC＝323℃，εr＝2648，tanδ＝1.45％。
As shown in fig. 1, the piezoelectric ceramic of example 1 is shown to have a perovskite structure.
As shown in FIG. 2, the dielectric thermogram of example 1 shows that the Curie temperature of the sample can reach 323 ℃.
Example 2
The molecular formula of the preparation formula is as follows:
0.99Pb0.97Sr0.02La0.01(Zr0.51Ti0.49)O3-0.01BiSbO3-0.1％wtCeO2-0.1％wtSm2O3the modified lead zirconate titanate piezoelectric ceramic added with the bismuth antimonate.
Wherein: u is 0.01, x is 0.02, y is 0.01, z is 0.51, v is 0.1, and h is 0.1.
The preparation method comprises the following steps:
the method comprises the following steps: with SrCO3、La2O3、ZrO2、TiO2、Sb2O3、Bi2O3、Pb 304、CeO2、Sm2O3Weighing Pb, Sr, La, Zr, Ti, Sb, Bi, Ce and Sm in the formula according to the stoichiometric ratio of Pb, Sr, La, Zr, Ti, Sb, Bi, Ce and Sm, and mixing in an alcohol solvent;
step two: grinding with zirconium ball for 24 hr, drying to obtain alcohol extract, and pre-sintering at 900 deg.C for 2 hr to obtain pre-sintered powder;
step three: performing secondary ball milling on the presintered powder in a ball milling tank, and performing secondary drying after performing roller milling for 13h to obtain dried powder;
step four: adding a PVA solution with the mass ratio of 8% into the secondarily dried powder, fully grinding and granulating, and pressing into small wafers at the pressure of 1.5 MPa;
step five: keeping the pressed small wafer at 750 ℃ for 2h for carrying out glue removing treatment, and keeping the sample at 1200 ℃ for 2h for sintering to obtain a ceramic wafer;
step six: covering silver paste on two ends of the ceramic wafer, then carrying out silver firing treatment at 650 ℃, then placing the ceramic wafer in an environment at 140 ℃, applying a 4kV/mm electric field, preserving heat for 30min, carrying out polarization treatment, obtaining the modified lead zirconate titanate piezoelectric ceramic with the additional bismuth antimonate after the polarization is finished, and standing for 24h to test corresponding electrical properties.
The main parameters are d33 ═ 594pC/N, TC＝279℃，εr＝2758，tanδ＝1.73％。
Example 3
The molecular formula of the preparation formula is as follows:
0.98Pb0.97Sr0.02La0.01(Zr0.53Ti0.47)O3-0.02BiSbO3-0.1％wtCeO2-0.1％wtSm2O3the modified lead zirconate titanate piezoelectric ceramic added with the bismuth antimonate.
Wherein: u is 0.02, x is 0.02, y is 0.01, z is 0.51, v is 0.1, and h is 0.1.
The preparation method comprises the following steps:
the method comprises the following steps: with SrCO3、La2O3、ZrO2、TiO2、Sb2O3、Bi2O3、Pb 304、CeO2、Sm2O3Weighing Pb, Sr, La, Zr, Ti, Sb, Bi, Ce and Sm in the formula according to the stoichiometric ratio of Pb, Sr, La, Zr, Ti, Sb, Bi, Ce and Sm, and mixing in an alcohol solvent;
step two: grinding with zirconium ball for 24 hr, drying to obtain alcohol extract, and pre-sintering at 900 deg.C for 2 hr to obtain pre-sintered powder;
step three: performing secondary ball milling on the presintered powder in a ball milling tank, and performing secondary drying after performing roller milling for 13h to obtain dried powder;
step four: adding a PVA solution with the mass ratio of 8% into the secondarily dried powder, fully grinding and granulating, and pressing into small wafers at the pressure of 1.5 MPa;
step five: keeping the pressed small wafer at 750 ℃ for 2h for carrying out glue removing treatment, and keeping the sample at 1200 ℃ for 2h for sintering to obtain a ceramic wafer;
step six: covering silver paste on two ends of the ceramic wafer, then carrying out silver firing treatment at 650 ℃, then placing the ceramic wafer in an environment at 140 ℃, applying a 4kV/mm electric field, preserving heat for 30min, carrying out polarization treatment, obtaining the modified lead zirconate titanate piezoelectric ceramic with the additional bismuth antimonate after the polarization is finished, and standing for 24h to test corresponding electrical properties.
Its main parameters are d33 ═ 578pC/N, TC＝294℃，εr＝2783，tanδ＝1.9％。
Using the above-mentioned (1-z) Pb1-x(SruLa1-u)x(ZryTi1-y)O3-zBiSbO3-vwt％CeO2-hwt％Sm2O3The bismuth antimonate-added modified lead zirconate titanate piezoelectric ceramic prepared according to the formula shows excellent comprehensive electrical properties, and a sample prepared according to the formula can obtain the same high-voltage electrical propertiesThe high distance temperature is kept, so that the material has high electromechanical conversion capacity and a wide applicable range, and meanwhile, the low dielectric loss and dielectric constant are beneficial to reducing the noise output.
The above description is only for the purpose of illustrating the technical solutions of the present invention and not for the purpose of limiting the same, and other modifications or equivalent substitutions made by those skilled in the art to the technical solutions of the present invention should be covered within the scope of the claims of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Claims (8)

1. The modified lead zirconate titanate piezoelectric ceramic with additional bismuth antimonate is characterized in that: the co-doping substitution of Sr \ La is carried out at the A site of the PZT ceramic, and BiSbO is added3And a small amount of CeO2And Sm2O3Carrying out doping modification, wherein the formula is as follows:
(1-u)Pb1-x-ySrxLay(ZrzTi1-z)O3-uBiSbO3-vwt％CeO2-hwt％Sm2O3
wherein: x is more than or equal to 0 and less than or equal to 0.5, y is more than or equal to 0 and less than or equal to 0.5, z is more than or equal to 0.3 and less than or equal to 0.7, u is more than or equal to 0 and less than or equal to 0.3, v is more than or equal to 0 and less than or equal to 0.3, and h is more than or equal to 0 and less than or equal to 0.3.
2. A preparation method of modified lead zirconate titanate piezoelectric ceramic with additional bismuth antimonate is characterized by comprising the following steps: which comprises the following steps:
the method comprises the following steps: with SrCO3、La2O3、ZrO2、TiO2、Sb2O3、Bi2O3、Pb304、CeO2、Sm2O3Weighing Pb, Sr, La, Zr, Ti, Sb, Bi, Ce and Sm in the formula according to the stoichiometric ratio of Pb, Sr, La, Zr, Ti, Sb, Bi, Ce and Sm, and mixing in an alcohol solvent;
step two: rolling and grinding by using zirconium balls, drying alcohol, and pre-burning after drying to obtain pre-burned powder;
step three: performing secondary ball milling on the presintered powder, and then performing secondary drying to obtain secondarily dried powder;
step four: adding PVA solution into the secondarily dried powder, fully grinding the powder, and pressing the powder into small wafers;
step five: performing glue discharging treatment on the pressed small round piece, and sintering the small round piece after glue discharging to obtain a ceramic piece;
step six: covering silver paste on two ends of the ceramic chip, then carrying out silver burning treatment, then carrying out polarization treatment on the ceramic chip after silver burning, obtaining the modified lead zirconate titanate piezoelectric ceramic with additional bismuth antimonate after polarization is finished, and carrying out testing after standing for a period of time.
3. The method for preparing the modified lead zirconate titanate piezoelectric ceramic with the addition of the bismuth antimonate according to claim 2, is characterized in that: in the second step, the time for tumbling the zirconium balls is 24 hours.
4. The method for preparing the modified lead zirconate titanate piezoelectric ceramic with the addition of the bismuth antimonate according to claim 2, is characterized in that: in the second step, the pre-sintering temperature is 900 ℃, and the heat preservation time is 2 hours.
5. The method for preparing the modified lead zirconate titanate piezoelectric ceramic with the addition of the bismuth antimonate according to claim 2, is characterized in that: in the third step, the time of the secondary ball milling is 13 hours.
6. The method for preparing the modified lead zirconate titanate piezoelectric ceramic with the addition of the bismuth antimonate according to claim 2, is characterized in that: in the fourth step, the mass ratio of the PVA solution is 8%, and the powder after the secondary drying is pressed into small wafers in 1.5 PMa.
7. The method for preparing the modified lead zirconate titanate piezoelectric ceramic with the addition of the bismuth antimonate according to claim 2, is characterized in that: in the fifth step, the temperature of the binder removal treatment is 750 ℃, the heat preservation time is 2 hours, the sintering temperature is 1200 ℃, and the heat preservation time is 2 hours.
8. The method for preparing the modified lead zirconate titanate piezoelectric ceramic with the addition of the bismuth antimonate according to claim 2, is characterized in that: in the sixth step, the silver burning temperature is 650 ℃, the polarization temperature is 140 ℃, the polarization voltage is 4kV/mm, the polarization heat preservation time is 30min, and the standing time is 24 h.
CN202111369115.4A 2021-11-18 2021-11-18 Modified lead zirconate titanate piezoelectric ceramic with additional bismuth antimonate and preparation method thereof Pending CN113979747A (en)

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