CN115385689A - Lead magnesium niobate-lead zirconate titanate based piezoelectric ceramic material and preparation method thereof - Google Patents

Lead magnesium niobate-lead zirconate titanate based piezoelectric ceramic material and preparation method thereof Download PDF

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CN115385689A
CN115385689A CN202210395272.0A CN202210395272A CN115385689A CN 115385689 A CN115385689 A CN 115385689A CN 202210395272 A CN202210395272 A CN 202210395272A CN 115385689 A CN115385689 A CN 115385689A
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汪尧进
李响
王书豪
王佳佳
游浩然
丁冠中
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Nanjing University of Science and Technology
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Abstract

The invention discloses a lead magnesium niobate-lead zirconate titanate based piezoelectric ceramic material and a preparation method thereof. The general formula of the piezoelectric ceramic material is as follows: pb 0.92 Sr 0.06 Ba 0.02 (Mg 1/ 3 Nb 2/3 ) 0.25 Ti 0.40 Zr 0.35 O 3 ‑xwt％MnCO 3 Wherein x is more than 0.0 and less than or equal to 1.0. The piezoelectric coefficient d33 of the lead magnesium niobate-lead zirconate titanate-based piezoelectric ceramic material prepared by the invention can reach 530pC/N, and the mechanical quality factor Qm can reach 624; the preparation process has simple steps, easy operation, good repeatability and high yield; powder with the same components is adopted as protective atmosphere to bury powder in the sintering process, so that the loss of elements is avoided.

Description

Lead magnesium niobate-lead zirconate titanate based piezoelectric ceramic material and preparation method thereof
Technical Field
The invention relates to the technical field of piezoelectric ceramic materials, in particular to a lead magnesium niobate-lead zirconate titanate-based piezoelectric ceramic material and a preparation method thereof.
Background
The piezoelectric ceramic is a functional ceramic material capable of realizing the interconversion between mechanical energy and electric energy, has unique dielectric, ferroelectric, piezoelectric and pyroelectric properties, is widely applied to devices such as medical ultrasonic transducers (medical imaging), underwater acoustic transducers (sonar), various sensors (such as accelerometers, magnetoelectric sensors and the like), drivers (scanning probe technology and the like), and is an indispensable part in modern industrial systems.
Perovskite ferroelectric materials have attracted much attention since the world due to their high piezoelectric properties and good electromechanical coupling coefficients. Among them, lead zirconate titanate (PZT) -based piezoelectric ceramics, which are excellent in overall performance and easy to produce, have once come to the public attention and are industrially mass-produced. But PZT piezoelectric ceramics have higher sintering temperature and lower Curie temperature, in order to make up the defects of PZT piezoelectric ceramics, PMN components with excellent dielectric property and lower sintering temperature are added into PZT piezoelectric ceramics to prepare ternary piezoelectric ceramics lead magnesium niobate-lead zirconate titanate (PMN-PZT), compared with PZT piezoelectric ceramics, PMN-PZT piezoelectric ceramics have more excellent dielectric property and piezoelectric property, lower sintering temperature is easy for large-scale industrial production, and higher Curie temperature leads the application range to be wider. However, PMN-PZT ceramics face two problems in application: (1) the high voltage electrical activity and the high Curie temperature can not be obtained simultaneously; (2) high voltage electrical activity and high mechanical quality factor are not compatible. Although piezoelectric ceramics with specific physical parameters can be selectively used in industry to meet practical requirements, the ability of piezoelectric devices to achieve higher performance levels in more complex environments is limited to some extent.
Therefore, how to prepare a piezoelectric ceramic with both high piezoelectric activity and high mechanical quality factor becomes important to expand the application range of piezoelectric devices and adapt to more complex use environments. The formation of the solid solution by the aliovalent doping is one of effective methods for regulating and controlling the electrical properties of the lead magnesium niobate-lead zirconate titanate piezoelectric ceramic. The hard doping causes the increase of oxygen vacancies, forms an internal bias field, inhibits the turnover of ferroelectric domains, generates a pinning effect, and improves the electrical performance of the elevator at the cost of sacrificing the piezoelectric and dielectric properties of the material; the soft doping causes lead vacancies to be increased, and the vacancies are easy to be captured, so that the ferroelectric domain is easier to turn over, and the ferroelectric becomes 'soft', thereby improving the piezoelectric activity of the material, but the mechanical quality factor is reduced.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a lead magnesium niobate-lead zirconate titanate-based piezoelectric ceramic material and a preparation method thereof. The piezoelectric coefficient d33 of the lead magnesium niobate-lead zirconate titanate-manganese carbonate piezoelectric ceramic prepared by the invention can reach 530pC/N, and the mechanical quality factor Qm can reach 624.
The technical scheme of the invention is as follows:
a lead magnesium niobate-lead zirconate titanate-based piezoelectric ceramic material has a general formula as follows:
Pb 0.92 Sr 0.06 Ba 0.02 (Mg 1/3 Nb 2/3 ) 0.25 Ti 0.40 Zr 0.35 O 3 -xwt％MnCO 3
wherein x is more than 0.0 and less than or equal to 1.0.
A preparation method of lead magnesium niobate-lead zirconate titanate-based piezoelectric ceramic material comprises the following steps:
(1) Preparation of MgNb 2 O 6 Precursor: according to MgNb 2 O 6 Weighing MgO and Nb according to the stoichiometric ratio 2 O 5 Mixing to obtain ball-milled material, adding water, ball-milling, drying, calcining to obtain MgNb 2 O 6 A precursor;
(2) Preparation of base Material Pb 0.92 Sr 0.06 Ba 0.02 (Mg 1/3 Nb 2/3 ) 0.25 Ti 0.40 Zr 0.35 O 3 : according to Pb 0.92 Sr 0.06 Ba 0.02 (Mg 1/3 Nb 2/3 ) 0.25 Ti 0.40 Zr 0.35 O 3 Weighing MgNb in a stoichiometric ratio 2 O 6 With PbO, baCO 3 、SrCO 3 、TiO 2 、ZrO 2 Mixing to obtain ball-milled material, adding water, ball-milling, drying and sintering to obtain base material Pb 0.92 Sr 0.06 Ba 0.02 (Mg 1/ 3 Nb 2/3 ) 0.25 Ti 0.40 Zr 0.35 O 3 Namely, a base material PMN-PZT;
(3) Preparing powder: according to Pb 0.92 Sr 0.06 Ba 0.02 (Mg 1/3 Nb 2/3 ) 0.25 Ti 0.40 Zr 0.35 O 3 -xwt％MnCO 3 Weighing the base material Pb obtained in the step (2) according to the metering ratio 0.92 Sr 0.06 Ba 0.02 (Mg 1/3 Nb 2/3 ) 0.25 Ti 0.40 Zr 0.35 O 3 With MnCO 3 Mixing to obtain a ball-milled material, adding water, ball-milling and drying to obtain powder;
(4) Preparing a blank body: adding a polyvinyl alcohol solution into the powder prepared in the step (3), and uniformly mixing to prepare a blank;
(5) Preparing a piezoelectric ceramic material: and (5) placing the blank obtained in the step (4) in a muffle furnace for glue discharging and sintering to obtain the lead magnesium niobate-lead zirconate titanate-based piezoelectric ceramic material.
Further, in the step (1), the MgO has an average particle size of 50nm and a melting point of 350 ℃; the Nb 2 O 5 Has an average particle diameter of 50nm and a melting point of 1520 ℃.
Further, in the steps (1) and (2), the ball milling speed is 200-300 r/min, the time is 12-24 h, and the mass ratio of the ball milling materials, the grinding balls and the water is 1:2:1.5; the drying temperature is 60-80 ℃ and the drying time is 10-12 h.
Further, in the step (1), the calcination is carried out by heating to 1100-1200 ℃ at 3-5 ℃/min and then preserving the heat for 4-5 h.
Further, in the step (2), the TiO 2 Is anatase phase.
Further, in the step (2), the sintering is carried out by heating to 1250-1300 ℃ at the speed of 3-5 ℃/min and preserving the heat for 2-3 h.
Further, in the step (3), the MnCO 3 The purity of the product is more than or equal to 99 percent; the ball milling speed is 200-300 r/min, the time is 12-24 h, and the mass ratio of ball milling materials, grinding balls and water is 1:2:1.5; the drying temperature is 80-100 ℃, and the drying time is 10-12 h.
Further, in the step (4), the concentration of the polyvinyl alcohol solution is 5-10 wt%; the mass ratio of the polyvinyl alcohol solution to the powder is (1:9) - (2:8); the preparation process of the blank body comprises the following steps: granulating and compacting the mixed solution of the powder and the polyvinyl alcohol solution to obtain a blank; the green compact is pressed into a cylindrical green body with the diameter of 10mm and the thickness of 1mm under the pressure of 8-12 MPa.
Further, in the step (5), the conditions for discharging the glue are as follows: heating to 560-620 ℃ at the speed of 2-3 ℃/min, and keeping the temperature for 2-4 h; the sintering is carried out by heating to 1250-1300 ℃ at the speed of 5 ℃/min and keeping the temperature for 2-3 h.
The beneficial technical effects of the invention are as follows:
(1) The invention introduces MnCO into a PMN-PZT system 3 By regulating and controlling components, the comprehensive performance (d 33=530pC/N, qm = 624) of the material is effectively improved, and the material has obvious relaxation characteristics, so that the further development of the lead-based ceramic material is promoted.
(2) The method has the advantages of low cost of raw materials, simple process steps, easy operation, good repeatability and high yield; powder with the same components is adopted as protective atmosphere to bury powder in the sintering process, so that the loss of elements is avoided.
(3) The invention utilizes MnCO 3 The hardening effect caused by adding PMN-PZT modifies the piezoelectric ceramics, and the specific explanation of the hardening effect is as follows: mn 2+ Ion entry into PMN-PZT lattice to replace Zr in B-position of PMN-PZT 4+ Ions and Ti 4+ Ions are generated, and the same amount of oxygen vacancies, part of oxygen vacancies and Mn are generated in order to maintain electrical neutrality 2+ The ions are combined to generate defective dipoles, oxygen vacancies and the defective dipoles are jointly gathered at the domain wall of the piezoelectric ceramic to pin the domain wall motion, so that the piezoelectric ceramic is hardened, and macroscopically, the piezoelectric coefficient and the dielectric loss of the piezoelectric ceramic are reduced, and the coercive field and the mechanical quality factor are increased.Under the combined action of oxygen vacancies and defective dipoles, the mechanical quality factor of the piezoelectric ceramic is remarkably improved while a small amount of piezoelectric constants are sacrificed, and the comprehensive performance of the PMN-PZT ceramic is optimized.
Drawings
FIG. 1 is an X-ray diffraction pattern of a ceramic material prepared according to examples of the present invention and a ceramic material prepared according to a comparative example.
FIG. 2 is a graph showing the change of piezoelectric constant and mechanical quality factor with respect to composition of ceramic materials prepared in examples of the present invention and comparative examples.
FIG. 3 is a graph showing the change of planar electromechanical coupling coefficient with respect to composition of ceramic materials prepared in examples of the present invention and comparative examples.
Detailed Description
The invention is described in detail below with reference to the figures and examples.
Example 1
Lead magnesium niobate-lead zirconate titanate based piezoceramic material PMN-PZT-0.1wt% MnCO 3 The preparation method comprises the following steps:
(1) Preparation of precursor MgNb 2 O 6
According to MgNb 2 O 6 Weighing MgO (with average particle diameter of 50nm and melting point of 350 deg.C) and Nb according to a certain ratio 2 O 5 (average particle diameter of 50nm, melting point of 1520 ℃ C.), mixing MgO with Nb 2 O 5 Mixing to obtain ball-milled materials, adding water, and ball-milling for 24 hours at a speed of 300r/min, wherein the mass ratio of the ball-milled materials to the grinding balls to the water is 1:2:1.5, drying at 60 ℃ for 12h, calcining in a muffle furnace at 1200 ℃ and keeping the temperature for 4h (the temperature rise rate of the calcination is 5 ℃/min), thus obtaining a precursor MgNb 2 O 6 ；
(2) Preparation of base Material Pb 0.92 Sr 0.06 Ba 0.02 (Mg 1/3 Nb 2/3 ) 0.25 Ti 0.40 Zr 0.35 O 3
According to Pb 0.92 Sr 0.06 Ba 0.02 (Mg 1/3 Nb 2/3 ) 0.25 Ti 0.40 Zr 0.35 O 3 Weighing MgNb in a stoichiometric ratio 2 O 6 With PbO (yellow lead oxide), baCO 3 、SrCO 3 、TiO 2 (anatase phase), zrO 2 After ball milling materials are obtained by mixing, adding water to perform ball milling for 24 hours at the speed of 300r/min, wherein the mass ratio of the ball milling materials to the grinding balls to the water is 1:2:1.5, drying at 60 ℃ for 12 hours, placing in a muffle furnace at 1250 ℃ for sintering and preserving heat for 2 hours (the temperature rise rate of sintering is 5 ℃/min), and preparing a base material PMN-PZT;
(3) Preparation of the powder
According to PMN-PZT-0.1wt% MnCO 3 Weighing the base materials PMN-PZT and MnCO obtained in the step (2) according to the metering ratio 3 And after mixing to obtain ball-milled materials, adding water to perform ball milling for 24 hours at the speed of 300r/min, wherein the mass ratio of the ball-milled materials to the grinding balls to the water is 1:2:1.5, baking for 12 hours in an oven at the temperature of 80 ℃ to prepare powder;
(4) Preparation of a green body
Adding a polyvinyl alcohol aqueous solution (7 wt%) into the powder prepared in the step (3), wherein the mass ratio of the polyvinyl alcohol aqueous solution to the powder is 1:9; mixing, granulating, and pressing under 10MPa to obtain cylindrical blank with diameter of 10mm and thickness of 1 mm.
(5) Preparing the piezoelectric ceramic material
And (5) placing the blank obtained in the step (4) in a muffle furnace for glue discharging and sintering to obtain the lead magnesium niobate-lead zirconate titanate-based piezoelectric ceramic material.
The conditions for rubber discharge are as follows: the heating rate is 2 ℃/min, the glue discharging temperature is 600 ℃, and the heat preservation time is 2h.
The temperature rise rate of sintering is 5 ℃/min, the sintering temperature is 1250 ℃, and the heat preservation time is 2h; in order to avoid element loss, powder with the same components is used as protective atmosphere for powder burying in the sintering process.
Example 2
Lead magnesium niobate-lead zirconate titanate based piezoceramic material PMN-PZT-0.3wt% MnCO 3 The preparation method comprises the following steps:
(1) Preparation of precursor MgNb 2 O 6
According to MgNb 2 O 6 Weighing MgO (with average particle diameter of 50nm and melting point of 350 deg.C) and Nb according to a certain ratio 2 O 5 (average ofParticle size of 50nm, melting point 1520 deg.C), mixing MgO with Nb 2 O 5 Mixing to obtain ball-milled materials, adding water, and ball-milling for 24 hours at a speed of 300r/min, wherein the mass ratio of the ball-milled materials to the grinding balls to the water is 1:2:1.5, drying at 60 ℃ for 12h, calcining in a muffle furnace at 1200 ℃ and keeping the temperature for 4h (the temperature rise rate of the calcination is 5 ℃/min), thus obtaining a precursor MgNb 2 O 6 ；
(2) Preparation of base Material Pb 0.92 Sr 0.06 Ba 0.02 (Mg 1/3 Nb 2/3 ) 0.25 Ti 0.40 Zr 0.35 O 3
According to Pb 0.92 Sr 0.06 Ba 0.02 (Mg 1/3 Nb 2/3 ) 0.25 Ti 0.40 Zr 0.35 O 3 Weighing MgNb in a certain ratio 2 O 6 With PbO (yellow lead oxide), baCO 3 、SrCO 3 、TiO 2 (anatase phase), zrO 2 After ball milling materials are obtained by mixing, adding water to perform ball milling for 24 hours at the speed of 300r/min, wherein the mass ratio of the ball milling materials to the grinding balls to the water is 1:2:1.5, drying at 60 ℃ for 12h, placing in a muffle furnace at 1250 ℃ for sintering and preserving heat for 2h (the temperature rise rate of sintering is 5 ℃/min), and preparing a base material PMN-PZT;
(3) Preparation of the powder
According to PMN-PZT-0.3wt.% MnCO 3 Weighing the base materials PMN-PZT and MnCO obtained in the step (2) according to the metering ratio 3 After ball milling materials are obtained by mixing, adding water to perform ball milling for 24 hours at the speed of 300r/min, wherein the mass ratio of the ball milling materials to the grinding balls to the water is 1:2:1.5, baking for 12 hours in an oven at the temperature of 80 ℃ to prepare powder;
(4) Preparation of a green body
Adding a polyvinyl alcohol aqueous solution (7 wt%) into the powder prepared in the step (3), wherein the mass ratio of the polyvinyl alcohol aqueous solution to the powder is 1:9; mixing, granulating, and pressing under 10MPa to obtain cylindrical blank with diameter of 10mm and thickness of 1 mm.
(5) Preparing the piezoelectric ceramic material
And (5) placing the blank obtained in the step (4) in a muffle furnace for glue discharging and sintering to obtain the lead magnesium niobate-lead zirconate titanate-based piezoelectric ceramic material.
The rubber discharge conditions are as follows: the heating rate is 2 ℃/min, the glue discharging temperature is 600 ℃, and the heat preservation time is 2h.
The temperature rise rate of sintering is 5 ℃/min, the sintering temperature is 1270 ℃, and the heat preservation time is 2h; in order to avoid element loss, powder with the same components is adopted as protective atmosphere to bury powder in the sintering process.
Example 3
Lead magnesium niobate-lead zirconate titanate based piezoceramic material PMN-PZT-0.5wt% 3 The preparation method comprises the following steps:
(1) Preparation of precursor MgNb 2 O 6
According to MgNb 2 O 6 Weighing MgO (with average particle diameter of 50nm and melting point of 350 deg.C) and Nb according to a certain ratio 2 O 5 (average particle diameter of 50nm, melting point of 1520 ℃ C.), mixing MgO with Nb 2 O 5 Mixing to obtain ball-milled materials, adding water, and ball-milling for 24 hours at a speed of 300r/min, wherein the mass ratio of the ball-milled materials to the grinding balls to the water is 1:2:1.5, drying at 60 ℃ for 12h, calcining in a muffle furnace at 1200 ℃ and keeping the temperature for 4h (the temperature rise rate of the calcination is 5 ℃/min), thus obtaining a precursor MgNb 2 O 6 ；
(2) Preparation of base Material Pb 0.92 Sr 0.06 Ba 0.02 (Mg 1/3 Nb 2/3 ) 0.25 Ti 0.40 Zr 0.35 O 3
According to Pb 0.92 Sr 0.06 Ba 0.02 (Mg 1/3 Nb 2/3 ) 0.25 Ti 0.40 Zr 0.35 O 3 Weighing MgNb in a stoichiometric ratio 2 O 6 With PbO (yellow lead oxide), baCO 3 、SrCO 3 、TiO 2 (anatase phase), zrO 2 And after mixing to obtain ball-milled materials, adding water to perform ball milling for 24 hours at the speed of 300r/min, wherein the mass ratio of the ball-milled materials to the grinding balls to the water is 1:2:1.5, drying at 60 ℃ for 12h, placing in a muffle furnace at 1250 ℃ for sintering and preserving heat for 2h (the temperature rise rate of sintering is 5 ℃/min), and preparing a base material PMN-PZT;
(3) Preparation of the powder
According to PMN-PZT-0.5wt.% MnCO 3 Weighing the base materials PMN-PZT and MnCO obtained in the step (2) according to the metering ratio 3 After ball milling materials are obtained, adding water to perform ball milling for 24 hours at the speed of 300r/min, wherein the mass ratio of the ball milling materials to the grinding balls to the water is 1:2:1.5, baking for 12 hours in an oven at the temperature of 80 ℃ to prepare powder;
(4) Preparation of a green body
Adding a polyvinyl alcohol aqueous solution (7 wt%) into the powder prepared in the step (3), wherein the mass ratio of the polyvinyl alcohol aqueous solution to the powder is 1:9; mixing, granulating, and pressing under 10MPa to obtain cylindrical blank with diameter of 10mm and thickness of 1 mm.
(5) Preparing the piezoelectric ceramic material
And (5) placing the blank obtained in the step (4) in a muffle furnace for glue discharging and sintering to obtain the lead magnesium niobate-lead zirconate titanate-based piezoelectric ceramic material.
The conditions for rubber discharge are as follows: the heating rate is 2 ℃/min, the glue discharging temperature is 600 ℃, and the heat preservation time is 2h.
The temperature rise rate of sintering is 5 ℃/min, the sintering temperature is 1300 ℃, and the heat preservation time is 2h; in order to avoid element loss, powder with the same components is adopted as protective atmosphere to bury powder in the sintering process.
Example 4
Lead magnesium niobate-lead zirconate titanate based piezoceramic material PMN-PZT-0.8wt% MnCO 3 The preparation method comprises the following steps:
(1) Preparation of precursor MgNb 2 O 6
According to MgNb 2 O 6 Weighing MgO (with average particle diameter of 50nm and melting point of 350 deg.C) and Nb according to a certain ratio 2 O 5 (average particle diameter of 50nm, melting point of 1520 ℃ C.), mixing MgO with Nb 2 O 5 Mixing to obtain ball-milled materials, adding water, and ball-milling for 24 hours at a speed of 300r/min, wherein the mass ratio of the ball-milled materials to the grinding balls to the water is 1:2:1.5, drying at 60 ℃ for 12h, calcining in a muffle furnace at 1200 ℃ and keeping the temperature for 4h (the temperature rise rate of the calcination is 5 ℃/min), thus obtaining a precursor MgNb 2 O 6 ；
(2) Preparation of base Material Pb 0.92 Sr 0.06 Ba 0.02 (Mg 1/3 Nb 2/3 ) 0.25 Ti 0.40 Zr 0.35 O 3
According to Pb 0.92 Sr 0.06 Ba 0.02 (Mg 1/3 Nb 2/3 ) 0.25 Ti 0.40 Zr 0.35 O 3 Weighing MgNb in a certain ratio 2 O 6 With PbO (yellow lead oxide), baCO 3 、SrCO 3 、TiO 2 (anatase phase), zrO 2 After ball milling materials are obtained by mixing, adding water to perform ball milling for 24 hours at the speed of 300r/min, wherein the mass ratio of the ball milling materials to the grinding balls to the water is 1:2:1.5, drying at 60 ℃ for 12h, placing in a muffle furnace at 1250 ℃ for sintering and preserving heat for 2h (the temperature rise rate of sintering is 5 ℃/min), and preparing a base material PMN-PZT;
(3) Preparation of the powder
According to PMN-PZT-0.8wt% MnCO 3 Weighing the base materials PMN-PZT and MnCO obtained in the step (2) according to the metering ratio 3 And after mixing to obtain ball-milled materials, adding water to perform ball milling for 24 hours at the speed of 300r/min, wherein the mass ratio of the ball-milled materials to the grinding balls to the water is 1:2:1.5, baking for 12 hours in an oven at the temperature of 80 ℃ to prepare powder;
(4) Preparation of a green body
Adding a polyvinyl alcohol aqueous solution (7 wt%) into the powder prepared in the step (3), wherein the mass ratio of the polyvinyl alcohol aqueous solution to the powder is 1:9; mixing, granulating, and pressing under 10MPa to obtain cylindrical blank with diameter of 10mm and thickness of 1 mm.
(5) Preparing the piezoelectric ceramic material
And (5) placing the blank obtained in the step (4) in a muffle furnace for glue discharging and sintering to obtain the lead magnesium niobate-lead zirconate titanate-based piezoelectric ceramic material.
The conditions for rubber discharge are as follows: the heating rate is 2 ℃/min, the glue discharging temperature is 600 ℃, and the heat preservation time is 2h.
The temperature rise rate of sintering is 5 ℃/min, the sintering temperature is 1300 ℃, and the heat preservation time is 2h; in order to avoid element loss, powder with the same components is adopted as protective atmosphere to bury powder in the sintering process.
Example 5
Niobium magnesiumAcid lead-lead zirconate titanate-lead-based piezoceramic material PMN-PZT-1.0wt%, (MnCO) 3 The preparation method comprises the following steps:
(1) Preparation of precursor MgNb 2 O 6
According to MgNb 2 O 6 Weighing MgO (with average particle diameter of 50nm and melting point of 350 deg.C) and Nb according to a certain ratio 2 O 5 (average particle diameter of 50nm, melting point of 1520 ℃ C.), mixing MgO with Nb 2 O 5 Mixing to obtain ball-milled materials, adding water, and ball-milling for 24 hours at a speed of 300r/min, wherein the mass ratio of the ball-milled materials to the grinding balls to the water is 1:2:1.5, drying at 60 ℃ for 12h, calcining in a muffle furnace at 1200 ℃ and keeping the temperature for 4h (the temperature rise rate of the calcination is 5 ℃/min), thus obtaining a precursor MgNb 2 O 6 ；
(2) Preparation of base Material Pb 0.92 Sr 0.06 Ba 0.02 (Mg 1/3 Nb 2/3 ) 0.25 Ti 0.40 Zr 0.35 O 3
According to Pb 0.92 Sr 0.06 Ba 0.02 (Mg 1/3 Nb 2/3 ) 0.25 Ti 0.40 Zr 0.35 O 3 Weighing MgNb in a stoichiometric ratio 2 O 6 With PbO (yellow lead oxide), baCO 3 、SrCO 3 、TiO 2 (anatase phase), zrO 2 And after mixing to obtain ball-milled materials, adding water to perform ball milling for 24 hours at the speed of 300r/min, wherein the mass ratio of the ball-milled materials to the grinding balls to the water is 1:2:1.5, drying at 60 ℃ for 12h, placing in a muffle furnace at 1250 ℃ for sintering and preserving heat for 2h (the temperature rise rate of sintering is 5 ℃/min), and preparing a base material PMN-PZT;
(3) Preparation of the powder
According to PMN-PZT-1.0wt% >, mnCO 3 Weighing the base materials PMN-PZT and MnCO obtained in the step (2) according to the metering ratio 3 And after mixing to obtain ball-milled materials, adding water to perform ball milling for 24 hours at the speed of 300r/min, wherein the mass ratio of the ball-milled materials to the grinding balls to the water is 1:2:1.5, baking for 12 hours in an oven at the temperature of 80 ℃ to prepare powder;
(4) Preparation of a green body
Adding a polyvinyl alcohol aqueous solution (7 wt%) into the powder prepared in the step (3), wherein the mass ratio of the polyvinyl alcohol aqueous solution to the powder is 1:9; mixing, granulating, and pressing under 10MPa to obtain cylindrical blank with diameter of 10mm and thickness of 1 mm.
(5) Preparing the piezoelectric ceramic material
And (5) placing the blank obtained in the step (4) in a muffle furnace for glue discharging and sintering to obtain the lead magnesium niobate-lead zirconate titanate-based piezoelectric ceramic material.
The conditions for rubber discharge are as follows: the heating rate is 2 ℃/min, the glue discharging temperature is 600 ℃, and the heat preservation time is 2h.
The temperature rise rate of sintering is 5 ℃/min, the sintering temperature is 1280 ℃, and the heat preservation time is 2h; in order to avoid element loss, powder with the same components is used as protective atmosphere for powder burying in the sintering process.
Example 6
A lead magnesium niobate-lead zirconate titanate-based piezoceramic material PMN-PZT-0.3wt% MnCO 3 The preparation method comprises the following steps:
(1) Preparation of precursor MgNb 2 O 6
According to MgNb 2 O 6 Weighing MgO (with average particle diameter of 50nm and melting point of 350 deg.C) and Nb according to a certain ratio 2 O 5 (average particle diameter: 50nm, melting point: 1520 ℃ C.), mixing MgO with Nb 2 O 5 Mixing to obtain ball-milled materials, adding water, and ball-milling for 24 hours at a speed of 200r/min, wherein the mass ratio of the ball-milled materials to the grinding balls to the water is 1:2:1.5, drying at 60 ℃ for 10h, calcining in a muffle furnace at 1200 ℃ and keeping the temperature for 4h (the temperature rise rate of the calcination is 5 ℃/min), thus obtaining a precursor MgNb 2 O 6 ；
(2) Preparation of base Material Pb 0.92 Sr 0.06 Ba 0.02 (Mg 1/3 Nb 2/3 ) 0.25 Ti 0.40 Zr 0.35 O 3
According to Pb 0.92 Sr 0.06 Ba 0.02 (Mg 1/3 Nb 2/3 ) 0.25 Ti 0.40 Zr 0.35 O 3 Weighing MgNb in a certain ratio 2 O 6 With PbO (yellow lead oxide), baCO 3 、SrCO 3 、TiO 2 (anatase phase), zrO 2 And after mixing to obtain ball-milled materials, adding water to perform ball milling for 24 hours at a speed of 200r/min, wherein the mass ratio of the ball-milled materials to the grinding balls to the water is 1:2:1.5, drying at 60 ℃ for 12h, placing in a muffle furnace at 1250 ℃ for sintering and preserving heat for 2h (the temperature rise rate of sintering is 5 ℃/min), and preparing a base material PMN-PZT;
(3) Preparation of the powder
According to PMN-PZT-0.3wt.% MnCO 3 Weighing the base materials PMN-PZT and MnCO obtained in the step (2) according to the metering ratio 3 And after mixing to obtain ball-milled materials, adding water to perform ball milling for 24 hours at a speed of 200r/min, wherein the mass ratio of the ball-milled materials to the grinding balls to the water is 1:2:1.5, baking for 12 hours in an oven at the temperature of 80 ℃ to prepare powder;
(4) Preparation of a green body
Adding a polyvinyl alcohol aqueous solution (7 wt%) into the powder prepared in the step (3), wherein the mass ratio of the polyvinyl alcohol aqueous solution to the powder is 2:8; mixing, granulating, and pressing under 10MPa to obtain cylindrical blank with diameter of 10mm and thickness of 1 mm.
(5) Preparing the piezoelectric ceramic material
And (5) placing the blank obtained in the step (4) in a muffle furnace for glue discharging and sintering to obtain the lead magnesium niobate-lead zirconate titanate-based piezoelectric ceramic material.
The conditions for rubber discharge are as follows: the heating rate is 2 ℃/min, the glue discharging temperature is 600 ℃, and the heat preservation time is 2h.
The temperature rise rate of sintering is 5 ℃/min, the sintering temperature is 1270 ℃, and the heat preservation time is 2h; in order to avoid element loss, powder with the same components is adopted as protective atmosphere to bury powder in the sintering process.
Example 7
Lead magnesium niobate-lead zirconate titanate based piezoceramic material PMN-PZT-0.3wt% MnCO 3 The preparation method comprises the following steps:
(1) Preparation of precursor MgNb 2 O 6
According to MgNb 2 O 6 Weighing MgO (with average particle diameter of 50nm and melting point of 350 deg.C) and Nb according to a certain ratio 2 O 5 (average particle diameter of 50nm, melting point of 1520 ℃ C.), mixing MgO withNb 2 O 5 Mixing to obtain ball-milled materials, adding water, and ball-milling for 20 hours at a speed of 250r/min, wherein the mass ratio of the ball-milled materials to the grinding balls to the water is 1:2:1.5, drying at 70 ℃ for 11h, calcining in a muffle furnace at 1150 ℃ and keeping the temperature for 4.5h (the temperature rise rate of the calcination is 5 ℃/min) to prepare a precursor MgNb 2 O 6 ；
(2) Preparation of base Material Pb 0.92 Sr 0.06 Ba 0.02 (Mg 1/3 Nb 2/3 ) 0.25 Ti 0.40 Zr 0.35 O 3
According to Pb 0.92 Sr 0.06 Ba 0.02 (Mg 1/3 Nb 2/3 ) 0.25 Ti 0.40 Zr 0.35 O 3 Weighing MgNb in a stoichiometric ratio 2 O 6 With PbO (yellow lead oxide), baCO 3 、SrCO 3 、TiO 2 (anatase phase), zrO 2 And after mixing to obtain ball-milled materials, adding water to perform ball milling for 20 hours at a speed of 250r/min, wherein the mass ratio of the ball-milled materials to the grinding balls to the water is 1:2:1.5, drying at 70 ℃ for 11h, placing in a muffle furnace at 1250 ℃ for sintering and preserving heat for 2h (the temperature rise rate of sintering is 5 ℃/min), and preparing a base material PMN-PZT;
(3) Preparation of the powder
According to PMN-PZT-0.3wt% MnCO 3 Weighing the base materials PMN-PZT and MnCO obtained in the step (2) according to the metering ratio 3 And after mixing to obtain ball-milled materials, adding water to perform ball milling for 20 hours at a speed of 250r/min, wherein the mass ratio of the ball-milled materials to the grinding balls to the water is 1:2:1.5, baking for 11 hours in a baking oven at the temperature of 90 ℃ to prepare powder;
(4) Preparation of a green body
Adding a polyvinyl alcohol aqueous solution (7 wt%) into the powder prepared in the step (3), wherein the mass ratio of the polyvinyl alcohol aqueous solution to the powder is 1:8; mixing, granulating, and pressing under 12MPa to obtain cylindrical blank with diameter of 10mm and thickness of 1 mm.
(5) Preparing the piezoelectric ceramic material
And (5) placing the blank obtained in the step (4) in a muffle furnace for glue discharging and sintering to obtain the lead magnesium niobate-lead zirconate titanate-based piezoelectric ceramic material.
The conditions for rubber discharge are as follows: the heating rate is 2 ℃/min, the glue discharging temperature is 580 ℃, and the heat preservation time is 3h.
The temperature rise rate of sintering is 5 ℃/min, the sintering temperature is 1270 ℃, and the heat preservation time is 2h; in order to avoid element loss, powder with the same components is adopted as protective atmosphere to bury powder in the sintering process.
Comparative example 1 (x = 0)
A preparation method of lead magnesium niobate-lead zirconate titanate-based piezoelectric ceramic material PMN-PZT comprises the following steps:
(1) Preparation of precursor MgNb 2 O 6
According to MgNb 2 O 6 Weighing MgO (with average particle diameter of 50nm and melting point of 350 deg.C) and Nb according to a certain ratio 2 O 5 (average particle diameter of 50nm, melting point of 1520 ℃ C.), mixing MgO with Nb 2 O 5 Mixing to obtain ball-milled materials, adding water, and ball-milling for 24 hours at the speed of 300r/min, wherein the mass ratio of the ball-milled materials to the grinding balls to the water is 1:2:1.5, drying at 80 ℃ for 10h, calcining in a muffle furnace at 1200 ℃ and keeping the temperature for 4h (the heating rate of the calcination is 5 ℃/min), thus obtaining a precursor MgNb 2 O 6 ；
(2) Preparation of base Material Pb 0.92 Sr 0.06 Ba 0.02 (Mg 1/3 Nb 2/3 ) 0.25 Ti 0.40 Zr 0.35 O 3
According to Pb 0.92 Sr 0.06 Ba 0.02 (Mg 1/3 Nb 2/3 ) 0.25 Ti 0.40 Zr 0.35 O 3 Weighing MgNb in a certain ratio 2 O 6 With PbO, baCO 3 、SrCO 3 、TiO 2 、ZrO 2 And after mixing to obtain ball-milled materials, adding water to perform ball milling for 24 hours at the speed of 300r/min, wherein the mass ratio of the ball-milled materials to the grinding balls to the water is 1:2:1.5, drying at 80 ℃ for 10h, placing in a muffle furnace at 1250 ℃ for sintering and preserving heat for 2h (the temperature rise rate of sintering is 5 ℃/min), and preparing a base material PMN-PZT;
(3) Preparation of the powder
Performing secondary ball milling on the powder obtained in the step (2) for 24 hours, and drying in an oven at 80 ℃ for 12 hours;
(4) Preparation of a green body
Adding a polyvinyl alcohol aqueous solution (7 wt%) into the powder prepared in the step (3), wherein the mass ratio of the polyvinyl alcohol aqueous solution to the powder is 1:9; mixing, granulating, and pressing under 10MPa to obtain cylindrical blank with diameter of 10mm and thickness of 1 mm.
(5) Preparing the piezoelectric ceramic material
And (5) placing the blank obtained in the step (4) in a muffle furnace for glue discharging and sintering to obtain the lead magnesium niobate-lead zirconate titanate-based piezoelectric ceramic material.
The conditions for rubber discharge are as follows: the heating rate is 2 ℃/min, the glue discharging temperature is 600 ℃, and the heat preservation time is 2h.
The temperature rise rate of sintering is 5 ℃/min, the sintering temperature is 1250 ℃, and the heat preservation time is 2h; in order to avoid element loss, powder with the same components is adopted as atmosphere compensation to bury powder in the sintering process.
Test example:
polishing, electrifying and polarizing the ceramic materials prepared in the examples 1-5 and the comparative example 1, wherein the polarizing electric field is 15-20 kV/cm, the polarizing time is 15min, and the polarizing temperature is 120 ℃; the piezoelectric properties of the products were measured as shown in Table 1.
TABLE 1
Figure BDA0003598646800000121
As can be seen from Table 1, when MnCO is used 3 When the doping amount is 0.5wt%, d33 of the piezoelectric ceramic is 530pC/N, Q m 624, has the best combination property when MnCO is used 3 When the doping amount is less than or exceeds 0.5wt%, the overall performance of the piezoelectric ceramic is continuously reduced.
FIG. 1 is an X-ray diffraction pattern of the ceramic material prepared by the present invention, FIG. 1 (a) is an XRD pattern measured at room temperature, the measurement range is 20-80 degrees, and FIG. 1 (b) is a partial enlarged view of 44-45 degrees. As can be seen from the data, with MnCO 3 The doping amount is increased, and the phase structure of the material is gradually changed from trigonal-tetragonal coexistence dominated by tetragonal phase to trigonal dominated by trigonal phaseThe tetragonal phase coexists, but the pure perovskite structure is always maintained, indicating that MnCO 3 The doping of (2) can form a stable solid solution.
FIG. 2 is a graph of piezoelectric constant of samples with different doping amounts, and it can be seen that as MnCO changes 3 With the increase of the doping amount, the piezoelectric constant shows the effect of increasing and then decreasing, and the mechanical quality factor is continuously increased.
FIG. 3 is a graph of electromechanical coupling coefficients for samples of different doping amounts, which can be seen with MnCO 3 The electromechanical coupling coefficient shows the effect of gradually reducing by increasing the doping amount.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that it is obvious to those skilled in the art that various modifications and improvements can be made without departing from the principle of the present invention, and these modifications and improvements should also be considered as the protection scope of the present invention.

Claims (10)

1. The lead magnesium niobate-lead zirconate titanate-based piezoelectric ceramic material is characterized by having the following general formula:
Pb 0.92 Sr 0.06 Ba 0.02 (Mg 1/3 Nb 2/3 ) 0.25 Ti 0.40 Zr 0.35 O 3 -xwt％MnCO 3
wherein x is more than 0.0 and less than or equal to 1.0.
2. A preparation method of lead magnesium niobate-lead zirconate titanate-based piezoelectric ceramic material is characterized by comprising the following steps:
(1) Preparation of MgNb 2 O 6 Precursor: according to MgNb 2 O 6 Weighing MgO and Nb according to the stoichiometric ratio 2 O 5 Mixing to obtain ball-milled material, adding water, ball-milling, drying, calcining to obtain MgNb 2 O 6 A precursor;
(2) Preparation of base Material Pb 0.92 Sr 0.06 Ba 0.02 (Mg 1/3 Nb 2/3 ) 0.25 Ti 0.40 Zr 0.35 O 3 : according to Pb 0.92 Sr 0.06 Ba 0.02 (Mg 1/3 Nb 2/3 ) 0.25 Ti 0.40 Zr 0.35 O 3 Weighing MgNb in a certain ratio 2 O 6 With PbO, baCO 3 、SrCO 3 、TiO 2 、ZrO 2 Mixing to obtain ball-milled material, adding water, ball-milling, drying and sintering to obtain base material Pb 0.92 Sr 0.06 Ba 0.02 (Mg 1/3 Nb 2/3 ) 0.25 Ti 0.40 Zr 0.35 O 3 ；
(3) Preparing powder: according to Pb 0.92 Sr 0.06 Ba 0.02 (Mg 1/3 Nb 2/3 ) 0.25 Ti 0.40 Zr 0.35 O 3 -xwt％MnCO 3 Weighing the base material Pb obtained in the step (2) according to the metering ratio 0.92 Sr 0.06 Ba 0.02 (Mg 1/3 Nb 2/3 ) 0.25 Ti 0.40 Zr 0.35 O 3 With MnCO 3 Mixing to obtain a ball-milled material, adding water, ball-milling and drying to obtain powder;
(4) Preparing a blank body: adding a polyvinyl alcohol solution into the powder prepared in the step (3), and uniformly mixing to prepare a blank;
(5) Preparing a piezoelectric ceramic material: and (5) placing the blank obtained in the step (4) in a muffle furnace for glue discharging and sintering to obtain the lead magnesium niobate-lead zirconate titanate-based piezoelectric ceramic material.
3. The method according to claim 2, wherein in the step (1), the MgO has an average particle size of 50nm and a melting point of 350 ℃; the Nb 2 O 5 Has an average particle diameter of 50nm and a melting point of 1520 ℃.
4. The preparation method according to claim 2, characterized in that in the steps (1) and (2), the ball milling speed is 200-300 r/min, the time is 12-24 h, and the mass ratio of the ball milling materials, the milling balls and the water in the ball milling is 1:2:1.5; the drying temperature is 60-80 ℃ and the drying time is 10-12 h.
5. The preparation method according to claim 2, wherein in the step (1), the calcination is carried out by heating to 1100-1200 ℃ at 3-5 ℃/min and then keeping the temperature for 4-5 h.
6. The method according to claim 2, wherein in the step (2), the TiO is 2 Is anatase phase.
7. The method according to claim 2, wherein in the step (2), the sintering is carried out by raising the temperature to 1250-300 ℃ at a rate of 3-5 ℃/min and keeping the temperature for 2-3 h.
8. The production method according to claim 2, wherein in the step (3), the MnCO is 3 The purity of the product is more than or equal to 99 percent; the ball milling speed is 200-300 r/min, the time is 12-24 h, and the mass ratio of ball milling materials to grinding balls to water in the ball milling is 1:2:1.5; the drying temperature is 80-100 ℃, and the drying time is 10-12 h.
9. The method according to claim 2, wherein in the step (4), the concentration of the polyvinyl alcohol solution is 5 to 10wt%; the mass ratio of the polyvinyl alcohol solution to the powder is (1:9) - (2:8); the preparation process of the blank body comprises the following steps: and granulating and compacting the mixed solution of the powder and the polyvinyl alcohol solution to obtain a blank.
10. The preparation method according to claim 2, wherein in the step (5), the conditions for discharging the gel are as follows: heating to 560-620 ℃ at the speed of 2-3 ℃/min, and keeping the temperature for 2-4 h; the sintering is carried out by heating to 1250-1300 ℃ at the speed of 5 ℃/min and keeping the temperature for 2-3 h.
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CN115849903A (en) * 2022-12-21 2023-03-28 惠州市鑫永诚光电科技有限公司 Composite pyroelectric ceramic material and preparation method thereof
CN115894020A (en) * 2022-12-23 2023-04-04 佛山仙湖实验室 PMNZT-based piezoelectric ceramic with high piezoelectric coefficient and preparation method and application thereof

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* Cited by examiner, † Cited by third party
Title
LI WANG ET AL.: "Investigation of Phase Structure and Electrical Properties of Doped PMN–PZT Ceramics Prepared by Different Methods" *
YONGKE YAN ET AL.: ""Role of Secondary Phase in High Power Piezoelectric PMN-PZT Ceramics" *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115849903A (en) * 2022-12-21 2023-03-28 惠州市鑫永诚光电科技有限公司 Composite pyroelectric ceramic material and preparation method thereof
CN115849903B (en) * 2022-12-21 2023-08-22 惠州市鑫永诚光电科技有限公司 Composite pyroelectric ceramic material and preparation method thereof
CN115894020A (en) * 2022-12-23 2023-04-04 佛山仙湖实验室 PMNZT-based piezoelectric ceramic with high piezoelectric coefficient and preparation method and application thereof
CN115894020B (en) * 2022-12-23 2023-12-19 佛山仙湖实验室 PMNZT-based piezoelectric ceramic with high piezoelectric coefficient and preparation method and application thereof

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