阅读说明：本技术 高居里温度“收发”两用型pzt三元系压电陶瓷材料及其制备方法 (high-Curie-temperature 'transmitting-receiving' dual-purpose PZT ternary system piezoelectric ceramic material and preparation method thereof ) 是由 黄碧 尹协琳 于 2020-11-25 设计创作，主要内容包括：本发明属于压电陶瓷技术领域,具体涉及一种高居里温度“收/发”两用型PZT-Pb(Sn-(2/3)Nb-(1/3))三元系压电陶瓷材料及其制备方法,该三元系压电陶瓷材料以锆钛酸铅和铌锡酸铅固溶体为主要成分,可不掺杂或可掺杂选自SiO-2、La-2O-3和MnO-2中的至少一种或几种添加物,该PZT-Pb(Sn-(2/3)Nb-(1/3))三元系压电陶瓷材料组成为：Pb(Zr-(1-x)Ti-x)1-y(Sn-(2/3)Nb-(1/3))yO-3+awt.％SiO-2+bwt.％La-2O-3+cwt.％MnO-2；其中,x＝0.35～0.65,y＝0.0～0.20,a＝0～0.2,b＝0～0.3,c＝0～0.1；本发明的陶瓷材料具有较高的压电应变常数d-(33)和机电耦合系数k-p,适中的介电常数和机械品质因数,是一种性能优良的“收/发”两用型压电陶瓷材料。(The invention belongs to the technical field of piezoelectric ceramics, and particularly relates to high-Curie-temperature 'receiving/transmitting' dual-purpose PZT-Pb (Sn) 2/3 Nb 1/3 ) The ternary piezoelectric ceramic material takes lead zirconate titanate and lead niobate stannate solid solution as main components, and can be undoped or doped with SiO 2 、La 2 O 3 And MnO 2 At least one or more additives of PZT-Pb (Sn) 2/3 Nb 1/3 ) The ternary system piezoelectric ceramic material comprises the following components: pb (Zr) 1‑x Ti x )1‑y(Sn 2/3 Nb 1/3 )yO 3 +awt.％SiO 2 +bwt.％La 2 O 3 +cwt.％MnO 2 (ii) a Wherein x is 0.35-0.65, y is 0.0-0.20, a is 0-0.2, and b is0 to 0.3, c is 0 to 0.1; the ceramic material of the invention has higher piezoelectric strain constant d 33 And an electromechanical coupling coefficient k p Moderate dielectric constant and mechanical quality factor, and is a 'receiving/transmitting' dual-purpose piezoelectric ceramic material with excellent performance.)

1. High Curie temperature 'transmitting-receiving' dual-purpose PZT-Pb (Sn)_2/3Nb_1/3) The ternary system piezoceramic material is characterized in that: the ternary system piezoelectric ceramic material takes lead zirconate titanate and lead niobium stannate solid solution as main components, and can be undoped or doped with SiO₂、La₂O₃And MnO₂At least one or more additives;

the high Curie temperature "Transmit-receive" dual-purpose PZT-Pb (Sn)_2/3Nb_1/3) The ternary system piezoelectric ceramic material comprises the following components:

Pb(Zr_1-xTi_x)1-y(Sn_2/3Nb_1/3)yO₃+awt.％SiO₂+bwt.％La₂O₃+cwt.％MnO₂(ii) a Wherein x is 0.35 to 0.65, y is 0.0 to 0.20, a is 0 to 0.2, b is 0 to 0.3, and c is 0 to 0.1.

2. The high curie temperature "transceiver" PZT-Pb (Sn) of claim 1_2/3Nb_1/3) The preparation method of the ternary system piezoelectric ceramic material is characterized by sequentially comprising the following steps of: the method comprises the steps of material mixing, synthesis, fine grinding, molding, plastic discharging, sintering, electrode mounting and polarization.

3. The high curie temperature "transceiver" PZT-Pb (Sn) of claim 2_2/3Nb_1/3) The preparation method of the ternary system piezoelectric ceramic material is characterized by comprising the following steps:

in the mixing process, zirconium balls or steel balls are used as media;

in the fine grinding process, zirconium balls are used for stirring and ball milling;

the firing step is sintering at the temperature of 1265-1325 ℃ for 1-4 h;

the conditions of the polarization step are: the temperature is 120-160 ℃, the voltage is 3-5 kV/mm, the time is 10-20 min, and the polarization is carried out by pressure maintaining, temperature reducing.

4. A high Curie temperature "Transmit" dual-purpose PZT-Pb (Sn) as claimed in claim 3_2/3Nb_1/3) The preparation method of the ternary system piezoelectric ceramic material is characterized by comprising the following specific steps of:

1) preparing materials: PZT-Pb (Sn) of the high Curie temperature "Transmit/Transmit" dual-purpose type_2/3Nb_1/3) Calculating the composition of the ternary system piezoelectric ceramic material and weighing various raw materials;

2) mixing materials: deionized water and zirconium balls or steel balls are used as media, mixed in proportion, and subjected to ball milling for 7-9 hours by a drum;

3) briquetting and synthesis: drying the mixed raw materials, briquetting and synthesizing: synthesizing for 2-4 h at the temperature of 800-900 ℃;

4) crushing and fine grinding: coarsely crushing the synthesized powder prepared in the step 3), and then finely grinding, wherein the fine grinding adopts stirring ball milling, mixing according to a proportion, and ball milling for 12-20 h;

5) and (3) granulation and forming: discharging and drying the ball-milled materials, adding a binder, granulating and molding;

6) plastic discharging: placing the molded sample in a box type electric furnace for plastic removal;

7) and (3) sintering: placing the sample into an alumina crucible for sealed sintering, wherein the sintering process is to preserve heat for 1-4 h under the temperature condition of 1265-1325 ℃;

8) machining: machining the sintered sample according to the specification requirement;

9) ultrasonic cleaning and upper electrode;

10) polarization: putting a sample with electrodes in silicon oil, and polarizing by a high-voltage electric field, wherein the polarizing conditions are as follows: the temperature is 120-160 ℃, the voltage is 3-5 kV/mm, and the time is 10-20 min.

5. The high Curie temperature "Transmit" dual-purpose PZT-Pb (Pb) (according to claim 4)Sn_2/3Nb_1/3) The preparation method of the ternary system piezoelectric ceramic material is characterized by comprising the following steps: the step 2) comprises the following steps: steel ball: deionized water 1: 2: mixing at a ratio of 0.6.

6. The high Curie temperature "Transmit" dual-purpose PZT-Pb (Sn) according to claim 4_2/3Nb_1/3) The preparation method of the ternary system piezoelectric ceramic material is characterized by comprising the following steps: the synthesis temperature in the step 3) is 830-880 ℃.

7. The high Curie temperature "Transmit" dual-purpose PZT-Pb (Sn) according to claim 4_2/3Nb_1/3) The preparation method of the ternary system piezoelectric ceramic material is characterized by comprising the following steps: in the step 4), the raw materials are as follows: zirconium ball: deionized water 1: 1.5: mixing at a ratio of 0.6.

Technical Field

The invention belongs to the technical field of piezoelectric ceramics, and particularly relates to high-Curie-temperature 'receiving/transmitting' dual-purpose PZT-Pb (Sn)_2/3Nb_1/3) Ternary system piezoelectric ceramic material and its preparation method.

Background

With the rapid development of modern science and technology, the research on the piezoelectric ceramic material is more and more intensive, and the application is more and more extensive, for example, when the piezoelectric transducer is designed, the piezoelectric ceramic element is often required to have the receiving and transmitting functions, and the piezoelectric ceramic element is expected to be used in the environment with higher temperature, which will provide a new challenge for the research on the piezoelectric ceramic, and it is difficult to obtain the "receiving/transmitting" dual-purpose piezoelectric ceramic with high curie temperature, high receiving sensitivity and stronger transmitting signal. At present, the most commonly used piezoelectric ceramic materials generally have a relatively low curie temperature (Tc), and easily cause material depolarization when the temperature rises, so that the piezoelectric performance of the transducer is unstable, and the like. The invention prepares the novel piezoelectric ceramic material with high Curie temperature, high receiving sensitivity and strong transmitting signal based on meeting the higher requirement of the receiving/transmitting dual-purpose piezoelectric device working in a high-temperature environment on the piezoelectric ceramic material.

Disclosure of Invention

Aiming at the defects of the prior art, the invention provides a receiving/transmitting dual-purpose piezoceramic material with high Curie temperature, high receiving sensitivity and strong transmitting signal, and the main performances of a material standard sheet (phi 20 multiplied by 1) are as follows: d₃₃＝430pC/N，ε_33T/ε_o＝1800，tanδ＝1.50％，k_p＝0.64，Q_m＝100，T_c358 ℃. Compared with common PZT piezoelectric ceramics of the same kind, the ceramic material of the invention has higher piezoelectric strain constant d₃₃And an electromechanical coupling coefficient k_pModerate dielectric constant and mechanical quality factor, and is a 'receiving/transmitting' dual-purpose piezoelectric ceramic material with excellent performance.

The invention is realized by the following technical scheme:

high Curie temperature 'transmitting-receiving' dual-purpose PZT-Pb (Sn)_2/3Nb_1/3) The ternary piezoelectric ceramic material takes lead zirconate titanate and lead niobate stannate solid solution as main components, and can be undoped or doped with SiO₂、La₂O₃And MnO₂At least one or more additives;

the high Curie temperature "Transmit-receive" dual-purpose PZT-Pb (Sn)_2/3Nb_1/3) The ternary system piezoelectric ceramic material comprises the following components:

Pb(Zr_1-xTi_x)1-y(Sn_2/3Nb_1/3)yO₃+awt.％SiO₂+bwt.％La₂O₃+cwt.％MnO₂(ii) a Wherein x is 0.35-0.65, y is 0.0-0.20, a is 0-0.2, b is 0-0.3, and c is 0-0.1; wherein x and y represent a molar ratio; a. b and c represent mass ratios.

High Curie temperature 'transmitting-receiving' dual-purpose PZT-Pb (Sn)_2/3Nb_1/3) The preparation method of the ternary system piezoelectric ceramic material sequentially comprises the following steps: the method comprises the steps of material mixing, synthesis, fine grinding, molding, plastic discharging, sintering, electrode mounting and polarization.

Preferably, zirconium balls or steel balls are used as media in the mixing process; in the fine grinding process, zirconium balls are used for stirring and ball milling; the firing step is sintering at the temperature of 1265-1325 ℃ for 1-4 h; the conditions of the polarization step are: the temperature is 120-160 ℃, the voltage is 3-5 kV/mm, the time is 10-20 min, and the polarization is carried out by pressure maintaining, temperature reducing.

Preferably, the specific steps are as follows:

1) preparing materials: PZT-Pb (Sn) of the high Curie temperature "Transmit/Transmit" dual-purpose type_2/3Nb_1/3) Calculating the composition of the ternary system piezoelectric ceramic material and weighing various raw materials;

2) mixing materials: deionized water and zirconium balls or steel balls are used as media, mixed in proportion, and subjected to ball milling for 7-9 hours by a drum;

3) briquetting and synthesis: drying the mixed raw materials, briquetting and synthesizing: synthesizing for 2-4 h at the temperature of 800-900 ℃;

4) crushing and fine grinding: coarsely crushing the synthesized powder prepared in the step 3), and then finely grinding, wherein the fine grinding adopts stirring ball milling, mixing according to a proportion, and ball milling for 12-20 h;

5) and (3) granulation and forming: discharging and drying the ball-milled materials, adding a binder, granulating and molding;

6) plastic discharging: placing the molded sample in a box type electric furnace for plastic removal;

7) and (3) sintering: placing the sample into an alumina crucible for sealed sintering, wherein the sintering process is to preserve heat for 1-4 h under the temperature condition of 1265-1325 ℃;

8) machining: machining the sintered sample according to the specification requirement;

9) ultrasonic cleaning and upper electrode;

10) polarization: putting a sample with electrodes in silicon oil, and polarizing by a high-voltage electric field, wherein the polarizing conditions are as follows: the temperature is 120-160 ℃, the voltage is 3-5 kV/mm, and the time is 10-20 min.

Preferably, in the step 2), the raw materials are as follows: steel ball: deionized water 1: 2: mixing at a ratio of 0.6.

Preferably, the synthesis temperature in the step 3) is 830-880 ℃.

Preferably, in the step 4), the raw materials are as follows: zirconium ball: deionized water 1: 1.5: mixing at a ratio of 0.6.

The invention has the beneficial effects that:

the invention obtains a receiving/transmitting dual-purpose piezoceramic material with high Curie temperature, high receiving sensitivity and strong transmitting signal, and the main performances of a material standard sheet (phi 20 multiplied by 1) are as follows: d₃₃＝430pC/N，ε_33T/ε_o＝1800，tanδ＝1.50％，k_p＝0.64，Q_m＝100，T_c358 ℃. Compared with common PZT piezoelectric ceramics of the same kind, the ceramic material of the invention has higher piezoelectric strain constant d₃₃And an electromechanical coupling coefficient k_pModerate dielectric constant and mechanical quality factor, and is a 'receiving/transmitting' dual-purpose piezoelectric ceramic material with excellent performance. The ternary system ceramic has the characteristic of being capable of widely adjusting the piezoelectric performance, the performance of the material can be greatly changed by changing different proportions of three components, and some modification additives can be added on the basis of the ternary system main components, so that the performance of the material is further improved;

the piezoelectric ceramic element made of the material can be used for manufacturing a petroleum flowmeter, and has high Curie temperaturePZT-Pb (Sn) for both receiving and transmitting_2/3Nb_1/3) A ternary system piezoelectric ceramic material;

the preparation method provided by the invention has the advantages of stable process, good repeatability, low cost, moderate sintering temperature and the like, the ceramic material prepared by the method is compact and uniform, can meet the requirements of different piezoelectric transceiver piezoelectric devices, and the product performance can completely replace similar imported products, thereby having good application prospect.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The first embodiment is as follows:

high curie temperature "send-receive" dual-purpose PZT-Pb (Sn)_2/3Nb_1/3) The ternary system piezoelectric ceramic material comprises the following components:

Pb(Zr_1-xTi_x)1-y(Sn_2/3Nb_1/3)yO₃+awt.％SiO₂+bwt.％La₂O₃+cwt.％MnO₂(ii) a Wherein x is 0.35, y is 0.20, a is 0, b is 0.2, and c is 0.1; wherein x and y represent a molar ratio; a. b and c represent mass ratios.

Specifically, the method comprises the following steps:

1) preparing materials: PZT-Pb (Sn) in terms of high Curie temperature "Transmit/Transmit" dual use_2/3Nb_1/3) Calculating the composition of the ternary system piezoelectric ceramic material and weighing various raw materials;

2) mixing materials: deionized water and zirconium balls or steel balls are used as media, and the raw materials are as follows: steel ball: deionized water 1: 2: mixing according to the proportion of 0.6, and ball-milling and mixing for 7-9 h by using a roller;

3) briquetting and synthesis: drying the mixed raw materials, briquetting and synthesizing: synthesizing for 2-4 h at 850 ℃;

4) crushing and fine grinding: coarsely crushing the synthesized powder prepared in the step 3), and then finely grinding, wherein the fine grinding adopts stirring ball milling, and the raw materials are as follows: zirconium ball: deionized water 1: 1.5: mixing according to the proportion of 0.6, and ball-milling for 12-20 h;

5) and (3) granulation and forming: discharging and drying the ball-milled materials, adding a binder, granulating and molding;

6) plastic discharging: placing the molded sample in a box type electric furnace for plastic removal;

7) and (3) sintering: placing the sample into an alumina crucible for sealed sintering, wherein the sintering process is to preserve heat for 1-4 h under the temperature condition of 1265-1325 ℃;

8) machining: machining the sintered sample according to the specification requirement;

9) ultrasonic cleaning and upper electrode;

10) polarization: putting a sample with electrodes in silicon oil, and polarizing by a high-voltage electric field, wherein the polarizing conditions are as follows: the temperature is 120-160 ℃, the voltage is 3-5 kV/mm, and the time is 10-20 min.

Example two:

high curie temperature "send-receive" dual-purpose PZT-Pb (Sn)_2/3Nb_1/3) The ternary system piezoelectric ceramic material comprises the following components:

Pb(Zr_1-xTi_x)1-y(Sn_2/3Nb_1/3)yO₃+awt.％SiO₂+bwt.％La₂O₃+cwt.％MnO₂(ii) a Wherein x is 0.50, y is 0.10, a is 0.1, b is 0.1, and c is 0.1; wherein x and y represent a molar ratio; a. b and c represent mass ratios.

Specifically, the method comprises the following steps:

1) preparing materials: PZT-Pb (Sn) in terms of high Curie temperature "Transmit/Transmit" dual use_2/3Nb_1/3) Calculating the composition of the ternary system piezoelectric ceramic material and weighing various raw materials;

2) mixing materials: deionized water and zirconium balls or steel balls are used as media, and the raw materials are as follows: steel ball: deionized water 1: 2: mixing according to the proportion of 0.6, and ball-milling and mixing for 7-9 h by using a roller;

3) briquetting and synthesis: drying the mixed raw materials, briquetting and synthesizing: synthesizing for 2-4 h at the temperature of 830 ℃;

4) crushing and fine grinding: coarsely crushing the synthesized powder prepared in the step 3), and then finely grinding, wherein the fine grinding adopts stirring ball milling, and the raw materials are as follows: zirconium ball: deionized water 1: 1.5: mixing according to the proportion of 0.6, and ball-milling for 12-20 h;

5) and (3) granulation and forming: discharging and drying the ball-milled materials, adding a binder, granulating and molding;

6) plastic discharging: placing the molded sample in a box type electric furnace for plastic removal;

7) and (3) sintering: placing the sample into an alumina crucible for sealed sintering, wherein the sintering process is to preserve heat for 1-4 h under the temperature condition of 1265-1325 ℃;

8) machining: machining the sintered sample according to the specification requirement;

9) ultrasonic cleaning and upper electrode;

10) polarization: putting a sample with electrodes in silicon oil, and polarizing by a high-voltage electric field, wherein the polarizing conditions are as follows: the temperature is 120-160 ℃, the voltage is 3-5 kV/mm, and the time is 10-20 min.

Example three:

high curie temperature "send-receive" dual-purpose PZT-Pb (Sn)_2/3Nb_1/3) The ternary system piezoelectric ceramic material comprises the following components:

Pb(Zr_1-xTi_x)1-y(Sn_2/3Nb_1/3)yO₃+awt.％SiO₂+bwt.％La₂O₃+cwt.％MnO₂(ii) a Wherein x is 0.40, y is 0.15, a is 0, b is 0.1, and c is 0.1; wherein x and y represent a molar ratio; a. b and c represent mass ratios.

Specifically, the method comprises the following steps:

1) preparing materials: PZT-Pb (Sn) in terms of high Curie temperature "Transmit/Transmit" dual use_2/3Nb_1/3) Calculating the composition of the ternary system piezoelectric ceramic material and weighing various raw materials;

2) mixing materials: deionized water and zirconium balls or steel balls are used as media, and the raw materials are as follows: steel ball: deionized water 1: 2: mixing according to the proportion of 0.6, and ball-milling and mixing for 7-9 h by using a roller;

3) briquetting and synthesis: drying the mixed raw materials, briquetting and synthesizing: synthesizing for 2-4 h at 880 ℃;

4) crushing and fine grinding: coarsely crushing the synthesized powder prepared in the step 3), and then finely grinding, wherein the fine grinding adopts stirring ball milling, mixing according to a proportion, and ball milling for 12-20 h;

5) and (3) granulation and forming: discharging and drying the ball-milled materials, adding a binder, granulating and molding;

6) plastic discharging: placing the molded sample in a box type electric furnace for plastic removal;

7) and (3) sintering: placing the sample into an alumina crucible for sealed sintering, wherein the sintering process is to preserve heat for 1-4 h under the temperature condition of 1265-1325 ℃;

8) machining: machining the sintered sample according to the specification requirement;

9) ultrasonic cleaning and upper electrode;

10) polarization: putting a sample with electrodes in silicon oil, and polarizing by a high-voltage electric field, wherein the polarizing conditions are as follows: the temperature is 120-160 ℃, the voltage is 3-5 kV/mm, and the time is 10-20 min.

Example four:

high curie temperature "send-receive" dual-purpose PZT-Pb (Sn)_2/3Nb_1/3) The ternary system piezoelectric ceramic material comprises the following components:

Pb(Zr_1-xTi_x)1-y(Sn_2/3Nb_1/3)yO₃+awt.％SiO₂+bwt.％La₂O₃+cwt.％MnO₂(ii) a Wherein x is 0.65, y is 0.20, a is 0.2, b is 0.3, and c is 0.1; wherein x and y represent a molar ratio; a. b and c represent mass ratios.

Specifically, the method comprises the following steps:

1) preparing materials: PZT-Pb (Sn) in terms of high Curie temperature "Transmit/Transmit" dual use_2/3Nb_1/3) Calculating the composition of the ternary system piezoelectric ceramic material and weighing various raw materials;

2) mixing materials: deionized water and zirconium balls or steel balls are used as media, and the raw materials are as follows: steel ball: deionized water 1: 2: mixing according to the proportion of 0.6, and ball-milling and mixing for 7-9 h by using a roller;

3) briquetting and synthesis: drying the mixed raw materials, briquetting and synthesizing: synthesizing for 2-4 h at 860 ℃;

4) crushing and fine grinding: coarsely crushing the synthesized powder prepared in the step 3), and then finely grinding, wherein the fine grinding adopts stirring ball milling, and the raw materials are as follows: zirconium ball: deionized water 1: 1.5: mixing according to the proportion of 0.6, and ball-milling for 12-20 h;

5) and (3) granulation and forming: discharging and drying the ball-milled materials, adding a binder, granulating and molding;

6) plastic discharging: placing the molded sample in a box type electric furnace for plastic removal;

7) and (3) sintering: placing the sample into an alumina crucible for sealed sintering, wherein the sintering process is to preserve heat for 1-4 h under the temperature condition of 1265-1325 ℃;

8) machining: machining the sintered sample according to the specification requirement;

9) ultrasonic cleaning and upper electrode;

10) polarization: putting a sample with electrodes in silicon oil, and polarizing by a high-voltage electric field, wherein the polarizing conditions are as follows: the temperature is 120-160 ℃, the voltage is 3-5 kV/mm, and the time is 10-20 min.

For the piezoelectric ceramic material prepared in the first embodiment, the piezoelectric performance measurement is performed, and the main performance of the material standard sheet (Φ 20 × 1) is as follows: d₃₃＝430pC/N，ε_33T/ε_o＝1800，tanδ＝1.50％，k_p＝0.64，Q_m＝100，T_c358 ℃. Compared with common PZT piezoelectric ceramics of the same kind, the ceramic material of the invention has higher piezoelectric strain constant d₃₃And an electromechanical coupling coefficient k_pModerate dielectric constant and mechanical quality factor, and is a 'receiving/transmitting' dual-purpose piezoelectric ceramic material with excellent performance.

The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.