Textured piezoelectric ceramic and method of making and use thereof

Abstract

This invention discloses a textured piezoelectric ceramic, its preparation method, and its applications, belonging to the field of piezoelectric ceramic materials technology. The method utilizes a PMS-PZT ternary solid solution with inherently high Qm and electromechanical coupling coefficient k to lay the foundation for comprehensive performance. Furthermore, a BZT seed template is introduced, and a high-texture piezoelectric ceramic is prepared using a template grain growth method. <001> Oriented PMS-PZT textured piezoelectric ceramics achieve a synergistic improvement in both high piezoelectric constant and high mechanical quality factor. The textured structure also reduces dielectric loss while retaining high Curie temperature characteristics. The fabrication process, through steps such as tape casting and stacking, enables the large-scale preparation of textured piezoelectric ceramic green bodies. The process is clear and highly controllable, providing a feasible path for industrial production and solving the challenge of achieving both soft and hard piezoelectric ceramics. This significantly contributes to the design and application of high-power piezoelectric ceramics.

Description

Technical Field

[0001] This invention belongs to the field of piezoelectric ceramic materials technology, and relates to a textured piezoelectric ceramic, its preparation method and application. Background Technology

[0002] Piezoelectric ceramics are a class of functional materials that enable the coupling and conversion of mechanical and electrical energy. They have a wide range of applications in advanced manufacturing, electronic information, and energy detection, such as piezoelectric actuators, ultrasonic motors, deep-well acoustic detection, transducers, and vibration sensors. Piezoelectric ceramic materials are the sensitive elements and core components of the entire system, and their properties are typically determined by their piezoelectric constant, dielectric constant, and mechanical quality factor (P0.05). Q m The high voltage performance ensures the functional strength of the device, while the low loss ensures the long-term stability of the device.

[0003] Based on their performance characteristics, piezoelectric ceramics can generally be divided into two main categories: "soft" and "hard." "Soft" piezoelectric ceramics possess high piezoelectric, dielectric, and electromechanical properties, and are mainly used in sensors, medical imaging, and filters. "Hard" piezoelectric ceramics have a high mechanical quality factor and low dielectric loss, making them core functional materials for high-power transmitting transducers, piezoelectric transformers, etc., and are widely used in sonar systems, ultrasonic detection, vibration control, and other electromechanical conversion systems.

[0004] However, under strong electric fields and high stress conditions, high-power piezoelectric ceramics experience significant energy losses, leading to increased temperature, decreased performance, and limited output power. Under resonant conditions, mechanical losses dominate in high-power piezoelectric ceramics, requiring a high mechanical quality factor (…). Q m Dielectric loss dominates under high electric field resonant conditions, requiring low dielectric loss and low polarization nonlinearity. Therefore, an ideal high-power piezoelectric ceramic must possess both "soft" and "hard" characteristics, that is, simultaneously have a high voltage coefficient (…). d 33 ),high Q m Low tanδ and high Curie temperature (T C To achieve high vibration velocity (v0∝) under harsh conditions such as high temperature, high pressure, and strong electric field. d 33 Q m It also boasts a wide operating temperature range. However, due to the inherent limitations of its ferroelectric domain structure, these properties are often contradictory; that is, while improving piezoelectric activity, it is usually accompanied by... Q mDecreasing performance, increased losses, and lower Curie temperature make it difficult to optimize the overall performance of both hardware and software. Summary of the Invention

[0005] To address the problems existing in the prior art, this invention provides a textured piezoelectric ceramic, its preparation method, and its application, thereby solving the technical problem that it is difficult to simultaneously achieve comprehensive performance of "both hard and soft" properties such as high voltage constant, high mechanical quality factor, low dielectric loss, and high Curie temperature in piezoelectric ceramics, and that there is a lack of scalable preparation process routes.

[0006] This invention is achieved through the following technical solution:

[0007] A method for preparing textured piezoelectric ceramics includes the following steps:

[0008] S1: Pb3O4, MnO2, ZrO2, TiO2, and Sb2O3 are mixed according to a ratio of 0.05Pb(MnO2) / 2. 1 / 3 Sb 2 / 3 After mixing O3-0.5PbZrO3-0.45PbTiO3 in a stoichiometric ratio, the mixture is subjected to ball milling, drying, grinding, and sieving once to obtain a raw material mixture. The raw material mixture is then pre-calcined to obtain pre-calcined powder. The pre-calcined powder is then subjected to ball milling, drying, grinding, and sieving twice to obtain PMS-PZT powder.

[0009] S2: CuO, PbO, dispersant, organic binder, plasticizer and solvent are added to the PMS-PZT powder, and ball milling is performed three times. After the ball milling is completed, BZT seed crystal template is added to obtain a slurry. The slurry is then subjected to tape casting, stacking and hot pressing treatment in sequence to obtain PMS-PZT textured piezoelectric ceramic green body.

[0010] S3: The PMS-PZT textured piezoelectric ceramic green body is subjected to cold isostatic pressing, sintering, polishing, silver plating and polarization treatment in sequence to obtain the textured piezoelectric ceramic.

[0011] Preferably, zirconium balls are used as grinding balls and anhydrous ethanol is used as the grinding medium in both the primary and secondary ball milling processes; the primary ball milling time is 18~48h; and the secondary ball milling time is 12~72h.

[0012] Preferably, the temperature for both primary and secondary drying is 80~100℃, and the time is 12~24h; the mesh size of the sieve is 80~200 mesh for both primary and secondary sieving.

[0013] Preferably, the pre-firing treatment specifically involves heating at a rate of 2~10℃ / min to 750℃~850℃ for 2~5 hours.

[0014] Preferably, in step S2, the amounts of CuO, PbO, dispersant, organic binder, plasticizer, and solvent added account for 0.05%~0.3%, 1.0%~3.0%, 0.5%~1.5%, 2.0%~4.0%, 0.5%~1.5%, and 8%~15% of the mass of PMS-PZT powder, respectively.

[0015] Preferably, in step S2, the amount of BZT seed template added is 1% to 5% of the PMS-PZT powder.

[0016] Preferably, in step S3, the pressure of cold isostatic pressing is 200~300MPa, and the time is 15~20min; the sintering treatment is specifically: heating to 1100~1300℃ at a heating rate of 2~5℃ / min, and sintering for 5~10h; the polishing treatment is to use 600~2000 grit sandpaper for grinding.

[0017] Preferably, in step S3, the silver plating process specifically involves: uniformly coating the polished surface with silver paste and placing it in a resistance furnace, holding it at a temperature of 500~850℃ for 5~60 minutes, and then allowing it to cool naturally to room temperature; in the polarization process, the polarization temperature is 90~150℃, the polarization voltage is 10~50kV / cm, and the polarization voltage holding time is 10~60 minutes.

[0018] A textured piezoelectric ceramic is prepared by the method described above; the crystallographic orientation of the textured piezoelectric ceramic is as follows: <001> Orientation, the Curie temperature of the textured piezoelectric ceramic is 299°C, and the piezoelectric constant is... d 33 Mechanical quality factor: 700~750 pC / N Q m The range is 690~720, with a strong field. E C The vibration voltage is 12.8 kV / cm, and the vibration velocity is 1.8 m / s.

[0019] The above-mentioned application of textured piezoelectric ceramics in sonar buoys.

[0020] Compared with the prior art, the present invention has the following beneficial technical effects:

[0021] This invention discloses a method for preparing textured piezoelectric ceramics. First, in the selection of the material system, Pb(Mn) is used. 1 / 3 Sb 2 / 3The PMS-PZT ternary solid solution, consisting of PbZrO3-PbTiO3, possesses high Qm (mechanical quality factor) and electromechanical coupling coefficient k, laying the foundation for achieving comprehensive performance. Furthermore, by introducing a BZT seed template and utilizing the template grain growth method, a high-texture PMS-PZT solution was successfully prepared. <001> Oriented PMS-PZT textured piezoelectric ceramics. <001> Oriented polarized trigonal textured PMS-PZT ceramics exhibit excellent piezoelectric properties by promoting polarization rotation through the formation of multi-domain states. Simultaneously, this system also possesses rigid properties, achieving a synergistic improvement in both piezoelectric constant and mechanical quality factor. Furthermore, the textured structure helps reduce dielectric loss, while retaining the high Curie temperature characteristic of the PMS-PZT system itself, thus meeting the requirements for high Curie temperatures. In terms of fabrication technology, this method achieves large-scale preparation of textured piezoelectric ceramic green bodies through steps such as tape casting, stacking, hot pressing, cold isostatic pressing, and sintering. The process flow is clear and highly controllable, providing a feasible path for industrial production. Therefore, this method not only solves the comprehensive performance challenge of piezoelectric ceramics achieving both soft and hard properties but also provides a scalable fabrication process, which is of great help to the design and application of high-power piezoelectric ceramics.

[0022] Furthermore, zirconium balls were used as grinding balls and anhydrous ethanol as the grinding medium in both the primary and secondary ball milling processes. The primary ball milling time was 18–48 hours, and the secondary ball milling time was 12–72 hours. The zirconium balls have high hardness and good wear resistance, which can ensure effective grinding of the raw materials during the ball milling process and make the raw materials more uniformly mixed. Anhydrous ethanol as the grinding medium can prevent the raw materials from undergoing chemical reactions during the ball milling process and ensure the chemical stability of the raw materials. The reasonable ball milling time can make the raw materials fully mixed and refined, laying the foundation for obtaining uniform pre-fired powder and finally obtaining high-performance textured piezoelectric ceramics.

[0023] Furthermore, the temperature for both primary and secondary drying is 80~100℃, and the time is 12~24h. Suitable drying temperature and time can ensure that the moisture in the raw materials is fully evaporated, avoiding the impact of residual moisture on subsequent processes and product performance. During primary and secondary sieving, the mesh size of the sieve is 80~200 mesh. A reasonable sieve mesh size can ensure that the particle size of the raw materials after sieving is uniform, remove excessively large or small particles, improve the purity and uniformity of the raw materials, and facilitate the acquisition of textured piezoelectric ceramics with uniform microstructure.

[0024] Furthermore, the pre-calcination treatment specifically involves heating the material to 750℃~850℃ at a rate of 2~10℃ / min for 2~5 hours. A suitable heating rate can prevent the raw material from cracking due to thermal stress caused by excessively rapid heating. The specific pre-calcination temperature and time range can enable the raw material to undergo appropriate chemical reactions, forming pre-calcined powder with a certain degree of crystallinity and activity, providing a good foundation for subsequent processes such as ball milling and sintering, and helping to improve the performance stability of the final product.

[0025] Furthermore, in step S2, the amounts of CuO, PbO, dispersant, organic binder, plasticizer, and solvent added account for 0.05%~0.3%, 1.0%~3.0%, 0.5%~1.5%, 2.0%~4.0%, 0.5%~1.5%, and 8%~15% of the mass of PMS-PZT powder, respectively. The appropriate amount of CuO added as a sintering aid can adjust the sintering characteristics of ceramics, promote grain growth and densification during sintering, improve the microstructure of ceramics, and thus optimize the comprehensive performance of textured piezoelectric ceramics. The dispersant, organic binder, and plasticizer synergistically optimize the rheology of the slurry and the flexibility of the green body. The amount of solvent ensures that the solid content of the slurry is moderate, which is conducive to casting and film formation. This ratio together ensures the high orientation degree, low dielectric loss, and excellent high-power performance of textured ceramics.

[0026] Furthermore, in step S2, the amount of BZT seed template added is 1% to 5% of the PMS-PZT powder. The BZT seed template is a key factor in achieving ceramic texture; an appropriate amount can guide grain growth along a specific direction during sintering, forming a texture with high density. <001> Orientation structure. This textured structure can significantly improve the piezoelectric properties of ceramics. By forming multi-domain states to promote polarization rotation, the ceramics can achieve a synergistic improvement in piezoelectric constant and mechanical quality factor while maintaining hardness, thus meeting the performance requirements of high-power piezoelectric ceramics.

[0027] Furthermore, in step S3, the cold isostatic pressing pressure is 200~300MPa, and the time is 15~20min. Appropriate cold isostatic pressing parameters ensure that the PMS-PZT textured piezoelectric ceramic green body is subjected to uniform pressure in all directions, improving the density and uniformity of the green body, reducing internal defects, and providing a guarantee for obtaining high-performance ceramics through subsequent sintering. In addition, the sintering treatment specifically involves heating to 1100~1300℃ at a heating rate of 2~5℃ / min and sintering for 5~10h. A reasonable heating rate can avoid the green body being damaged by internal defects. Rapid heating can cause cracks; specific sintering temperatures and time ranges allow ceramic grains to grow fully and become dense, forming a good microstructure and improving the mechanical and electrical properties of ceramics, such as increasing the mechanical quality factor and reducing dielectric loss; in addition, polishing is done with 600-2000 grit sandpaper, which can make the ceramic surface smooth and flat, reduce surface defects and roughness, improve the surface quality of ceramics, and facilitate subsequent silvering and polarization treatments, while also improving the performance stability of ceramics in practical applications.

[0028] Furthermore, in step S3, the silver plating process specifically involves: uniformly coating the polished surface with silver paste and placing it in a resistance furnace, holding it at a temperature of 500~850℃ for 5~60 minutes, and then allowing it to cool naturally to room temperature. In addition, the polarization process involves a polarization temperature of 90~150℃, a polarization voltage of 10~50kV / cm, and a polarization voltage holding time of 10~60 minutes. Appropriate silver plating temperature and holding time can ensure that the silver paste is fully sintered, forming a good silver electrode, ensuring good contact between the electrode and the ceramic, reducing contact resistance, and improving the electrical properties of the ceramic, such as improving polarization efficiency and the stability of piezoelectric properties. Attached Figure Description

[0029] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of the present invention and should not be regarded as a limitation on the scope. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.

[0030] Figure 1 Cross-sectional scanning electron microscope (SEM) images of the ordinary PMS-PZT piezoelectric ceramic (R-PMS-PZT) (a) prepared in Comparative Example 1 of the present invention and the textured piezoelectric ceramic (T-PMS-PZT) (b) prepared in Example 1 of the present invention.

[0031] Figure 2 The images show the XRD patterns of the ordinary PMS-PZT piezoelectric ceramic (R-PMS-PZT) prepared in Comparative Example 1 and the textured piezoelectric ceramic (T-PMS-PZT) prepared in Example 1 of this invention.

[0032] Figure 3 The graph shows the dielectric constant of the ordinary PMS-PZT piezoelectric ceramic (R-PMS-PZT) prepared in Comparative Example 1 and the textured piezoelectric ceramic (T-PMS-PZT) prepared in Example 1 as a function of temperature.

[0033] Figure 4 Hysteresis loops of the ordinary PMS-PZT piezoelectric ceramic (R-PMS-PZT) prepared in Comparative Example 1 and the textured piezoelectric ceramic (T-PMS-PZT) prepared in Example 1 of this invention;

[0034] Figure 5 Impedance diagram and phase angle of the textured piezoelectric ceramic (T-PMS-PZT) prepared in Example 1 of this invention;

[0035] Figure 6 The vibration velocity of the textured piezoelectric ceramic (T-PMS-PZT) prepared in Example 1 of the present invention. Detailed Implementation

[0036] To enable those skilled in the art to understand the features and effects of the present invention, the terms and expressions mentioned in the specification are explained and defined in general below. Unless otherwise specified, all technical and scientific terms used herein have the ordinary meaning understood by those skilled in the art regarding the present invention, and in case of conflict, the definitions in this specification shall prevail.

[0037] The theories or mechanisms described and disclosed herein, whether right or wrong, should not in any way limit the scope of the invention, that is, the contents of the invention can be implemented without being limited by any particular theory or mechanism.

[0038] In this document, all features defined by numerical ranges or percentage ranges, such as numerical values, quantities, contents, and concentrations, are for the sake of brevity and convenience only. Accordingly, descriptions of numerical ranges or percentage ranges should be considered as covering and specifically disclosing all possible sub-ranges and individual numerical values ​​(including integers and fractions) within those ranges.

[0039] For the sake of brevity, not all possible combinations of the technical features in each implementation scheme or embodiment are described herein. Therefore, as long as there is no contradiction in the combination of these technical features, the technical features in each implementation scheme or embodiment can be combined arbitrarily, and all possible combinations should be considered within the scope of this specification.

[0040] This invention provides a textured piezoelectric ceramic, wherein the textured piezoelectric ceramic has a perovskite structure and a molecular formula of 0.05Pb(Mn) 1 / 3 Sb 2 / 3The present invention uses BZT seed templates and template grain growth method to successfully prepare PMS-PZT piezoelectric ceramics with high texture.

[0041] Specifically, in this invention, the BZT seed crystal template refers to micron- or submicron-sized single crystal particles of barium zirconium titanate ((Ba,Zr)TiO3, abbreviated as BZT) with a perovskite structure, which are used as orientation-inducing cores in the template grain growth method. "Seed crystal" refers to a pre-synthesized single crystal particle with a specific crystal orientation and high crystallinity. "Template" refers to these seed crystals that do not melt or completely dissolve during ceramic sintering, but rather serve as a substrate for epitaxial growth, guiding the surrounding polycrystalline matrix to grow oriented along its lattice orientation; BZT is used because it is compatible with the target ceramic 0.05Pb(Mn) 1 / 3 Sb 2 / 3 PMS-PZT (0.5PbZrO3-0.45PbTiO3) has a similar perovskite crystal structure and matching lattice parameters, which can effectively reduce the interface energy of heteroepitaxial growth, thereby promoting the preferred orientation of PMS-PZT grains along a specific crystal direction. By introducing BZT seed templates and combining them with hot pressing sintering and other processes, PMS-PZT grains can be preferentially aligned along a specific crystal direction. <001> PMS-PZT piezoelectric ceramics with high orientation and texture.

[0042] This invention also provides a method for preparing textured piezoelectric ceramics, comprising the following steps:

[0043] S1: Pb3O4, MnO2, ZrO2, TiO2, and Sb2O3 are mixed according to a ratio of 0.05Pb(MnO2) / 2. 1 / 3 Sb 2 / 3 After mixing O3-0.5PbZrO3-0.45PbTiO3 in a stoichiometric ratio, the mixture is subjected to ball milling, drying, grinding, and sieving once to obtain a raw material mixture. The raw material mixture is then pre-calcined to obtain pre-calcined powder. The pre-calcined powder is then subjected to ball milling, drying, grinding, and sieving twice to obtain PMS-PZT powder.

[0044] S2: CuO, PbO, dispersant, organic binder, plasticizer and solvent are added to the PMS-PZT powder. After ball milling, BZT seed template is added to obtain a slurry. The slurry is then subjected to tape casting, stacking and hot pressing treatment in sequence to obtain PMS-PZT textured piezoelectric ceramic green body.

[0045] S3: The PMS-PZT textured piezoelectric ceramic green body is subjected to cold isostatic pressing, sintering, polishing, silver plating and polarization treatment in sequence to obtain the textured piezoelectric ceramic.

[0046] The above preparation process is as follows:

[0047] S1: Preparation of 0.05Pb(Mn) 1 / 3 Sb 2 / 3 The method for producing O3-0.5PbZrO3-0.45PbTiO3 powder (i.e., PMS-PZT powder) is as follows:

[0048] (1) Ingredients

[0049] According to 0.05Pb(Mn 1 / 3 Sb 2 / 3 The raw materials were prepared by stoichiometric ratio of Pb3O4-0.5PbZrO3-0.45PbTiO3 (PMS-PZT). 68.7915g of Pb3O4 (99% purity), 0.4362g of MnO2 (99% purity), 18.6757g of ZrO2 (99.9% purity), 10.7245g of TiO2 (99.9% purity), and 1.4265g of Sb2O3 (99% purity) were weighed out as raw materials. All raw materials were mixed thoroughly and placed in a nylon container. Using zirconium balls as grinding media and anhydrous ethanol as the milling medium, the mixture was milled for 18-48 hours to obtain a raw material mixture. The zirconium balls were separated, and the raw material mixture was dried at 80-100℃ for 12-24 hours. It was then ground in a mortar and pestle and passed through an 80-200 mesh sieve.

[0050] (2) Pre-firing

[0051] Place the raw material mixture after passing through an 80-200 mesh sieve in step (1) into an alumina crucible, compact it with an agate rod, cover it, place it in a resistance furnace, pre-calcine it at 750-850℃ for 2-5 hours with a heating rate of 2-10℃ / min, cool it naturally to room temperature, remove it from the furnace, grind it with a mortar and pestle to obtain pre-calcined powder.

[0052] (4) Secondary ball milling

[0053] The pre-calcined powder was placed in a nylon can and milled thoroughly for 12-72 hours using zirconium balls as grinding media and anhydrous ethanol as the milling medium at a speed of 150-300 rpm. The zirconium balls were then separated, and the pre-calcined powder was dried at 80-100℃ for 12-24 hours. The powder was then ground in a mortar and pestle and passed through an 80-200 mesh sieve to obtain 0.05Pb(Mn)2. 1 / 3 Sb 2 / 3 O3-0.5PbZrO3-0.45PbTiO3 powder, i.e. PMS-PZT powder;

[0054] S2: Preparation of 0.05Pb(Mn) 1 / 3 Sb 2 / 3 O3-0.5PbZrO3-0.45PbTiO3 textured piezoelectric ceramic green body:

[0055] (1) Preparation of slurry

[0056] Prepared using a plate-shaped BZT seed template via template grain growth (TGG) <001> Oriented PMS-PZT textured piezoelectric ceramics. Specifically, CuO, a sintering aid, is added to PMS-PZT powder, followed by a certain amount of PbO (lead volatilizes during sintering, so a certain amount of PbO is added here), along with a dispersant (castor oil), an organic binder (PVB), a plasticizer (butyl phthalate and polyethylene glycol), and a solvent (ethanol and xylene), and then ball-milled. Subsequently, a slurry is prepared by adding a BZT seed template using magnetic stirring.

[0057] The amounts of CuO, PbO, dispersant, organic binder, plasticizer, and solvent added account for 0.05%~0.3%, 1.0%~3.0%, 0.5%~1.5%, 2.0%~4.0%, 0.5%~1.5%, and 8%~15% of the mass of PMS-PZT powder, respectively. More preferably, the amounts of CuO, PbO, dispersant, organic binder, plasticizer, and solvent added account for 0.125%, 1.5%, 0.813%, 2.846%, 0.813%, and 10.163% of the mass of PMS-PZT powder, respectively.

[0058] The amount of BZT seed template added is 1% to 5% of the mass of PMS-PZT powder.

[0059] (2) Casting, stacking and hot pressing

[0060] In the tape casting process, to obtain ceramic film strips with uniform thickness, dense structure, and good green strength, this invention employs a precisely controlled scraper device to pull the substrate at a stable speed of 0.5 cm / s, while simultaneously setting the blade height precisely to 200 micrometers. The light gray film strip obtained through tape casting is cut into squares, stacked, and then hot-pressed at 80°C. The hot-pressed green body is heated to 550°C to remove the binder and organic matter, yielding a PMS-PZT textured piezoelectric ceramic green body.

[0061] S3: Preparation of PMS-PZT textured piezoelectric ceramics

[0062] (1) Cold isostatic pressing

[0063] The PMS-PZT textured piezoelectric ceramic green body is subjected to cold isostatic pressing at a pressure of 200~300MPa for 15~20min;

[0064] The cold isostatic pressing described in this invention is a forming process that improves the density and strength of ceramic green bodies by uniformly applying isotropic static pressure at room temperature.

[0065] (2) Pressureless closed sintering

[0066] The PMS-PZT textured piezoelectric ceramic green body after cold isostatic pressing is embedded in homogeneous powder, placed on a zirconia plate, and then placed in an alumina sealed sagger. The temperature is raised to 1100-1300℃ at a heating rate of 2-5℃ / min, sintered for 5-10 hours, and then naturally cooled to room temperature in the furnace to obtain the fired piezoelectric ceramic.

[0067] (3) Polishing

[0068] The upper and lower surfaces of the sintered piezoelectric ceramic were polished with 600-2000 grit sandpaper, and then polished with metallographic sandpaper to a thickness of 0.8-1.2 mm. After that, they were ultrasonically cleaned with deionized water and ethanol respectively, and then dried.

[0069] (4) Silver-plated electrode

[0070] The silver paste is evenly coated on the two polished surfaces and placed in a resistance furnace. The furnace is kept at 500~850℃ for 5~60 minutes and then allowed to cool naturally to room temperature to obtain the piezoelectric ceramic with silver electrode plating.

[0071] (5) Polarization

[0072] The silver-plated piezoelectric ceramic was immersed in silicone oil and polarized along its thickness using a DC or AC electric field. The polarization temperature was 90–150 °C, the polarization voltage was 10–50 kV / cm, and the polarization voltage was maintained for 10–60 min, yielding a product with the chemical formula 0.05Pb(Mn). 1 / 3 Sb 2 / 3 Textured piezoelectric ceramics of O3-0.5PbZrO3-0.45PbTiO3, namely high-textured PMS-PZT piezoelectric ceramics.

[0073] Texture refers to the degree to which the grain orientation in a polycrystalline material is concentrated relative to a macroscopic reference plane or direction; that is, the degree to which the grain orientation deviates from a random distribution. In piezoelectric ceramics, high texture can be fabricated by introducing seed crystal templates and utilizing template grain growth methods. <001> Oriented ceramics, with their ordered arrangement, significantly enhance the piezoelectric properties and mechanical quality factor of the material. The degree of texture directly affects the anisotropic properties of the material; high texture means more concentrated grain orientation, resulting in superior physical properties in specific directions, such as piezoelectric constant and electromechanical coupling coefficient. In this invention, the large-scale preparation of textured piezoelectric ceramic green bodies is achieved through processes such as tape casting, stacking, hot pressing, cold isostatic pressing, and sintering, providing a feasible path for industrial production.

[0074] This invention, through the Templated Grain Growth (TGG) method and controlled ceramic sintering process, has for the first time achieved... <001> High-power PMS-PZT textured piezoelectric ceramics with high orientation and excellent overall performance. <001> Oriented PMS-PZT textured piezoelectric ceramics possess high power performance, a high Curie temperature, and a combination of soft and hard properties. Their Curie temperature is 299℃, ensuring a stable piezoelectric constant. d 33 Given a value of 704pC / N, Q m It can also reach 694, and the piezoelectric constant d 33 The coercivity of high-texture PMS-PZT piezoelectric ceramics is 4.1 times that of ordinary piezoelectric ceramics. E C It can reach 12.8kV / cm and the vibration velocity can reach 1.8m / s, exhibiting good rigidity characteristics. <001> The successful fabrication of oriented PMS-PZT textured piezoelectric ceramics combines soft piezoelectric properties with hard, high-power characteristics, effectively solving the problem of piezoelectric constant. d 33 With mechanical quality factor Q m The present invention addresses the common problem of mutual constraints between Pb (Mn) and Mn. 1 / 3 Sb 2 / 3 The PMS-PZT ternary solid solution (PbO3-PbZrO3-PbTiO3) has high... Q m and electromechanical coupling coefficient k It is a relatively common high-power ceramic. And in Pb(Mn) 1 / 3Sb 2 / 3 Based on the O3-PbZrO3-PbTiO3 system, a BZT seed template was introduced, resulting in a higher texture. <001> Oriented PMS-PZT textured piezoelectric ceramics. <001> Oriented polarized trigonal textured PMS-PZT ceramics exhibit excellent piezoelectric properties due to engineered domains, i.e., by forming multi-domain states to promote polarization rotation. Furthermore, the system itself also possesses hardness. Therefore, <001> Oriented PMS-PZT textured piezoelectric ceramics have achieved high-power performance with excellent overall properties. They combine high Curie temperature, high softness and high hardness, making them promising for applications in power devices.

[0075] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Furthermore, it should be understood that after reading the teachings of this invention, those skilled in the art can make various alterations or modifications to the invention, and these equivalent forms also fall within the scope defined by the appended claims.

[0076] The following examples use instruments and equipment conventional in the art. Experimental methods in the following examples, unless otherwise specified, are generally performed under conventional conditions or as recommended by the manufacturer. All raw materials used in the following examples are conventional commercially available products with specifications conventional in the art. In this specification and the following examples, unless otherwise specified, "%" refers to weight percentage, "parts" refers to parts by weight, and "ratio" refers to weight proportion.

[0077] Example 1

[0078] A textured piezoelectric ceramic with the general formula: 0.05Pb(Mn) 1 / 3 Sb 2 / 3 O3-0.5PbZrO3-0.45PbTiO3. Its preparation method is as follows:

[0079] 1. Preparation of PMS-PZT powder:

[0080] (1) Ingredients

[0081] For 0.05Pb(Mn) 1 / 3 Sb 2 / 3 O3-0.5PbZrO3-0.45PbTiO3 samples, according to 0.05Pb(Mn) 1 / 3 Sb 2 / 3 The stoichiometry of O3-0.5PbZrO3-0.45PbTiO3 was determined by weighing 68.7915g of Pb3O4 (99% purity), 0.4362g of MnO2 (99% purity), 18.6757g of ZrO2 (99.9% purity), 10.7245g of TiO2 (99.9% purity), and 1.4265g of Sb2O3 (99% purity) as raw materials. The raw material mixture was placed in a nylon container and milled with zirconium balls as grinding balls and anhydrous ethanol as the milling medium. The mass ratio of anhydrous ethanol to the raw material mixture was 1:1.2. The mixture was milled at 250 rpm for 48 hours. The zirconium balls were separated, and the raw material mixture was dried in a drying oven at 80℃ for 14 hours. It was then ground in a mortar and pestle for 30 minutes and passed through an 80-mesh sieve.

[0082] (2) Pre-firing

[0083] The raw material mixture after passing through an 80-mesh sieve in step (1) is placed in an alumina crucible and compacted with an agate rod to a compaction density of 1.5 g / cm³.3 Cover the contents and place them in a resistance furnace. Heat the furnace to 750°C at a rate of 3°C / min for 5 hours. Allow the contents to cool naturally to room temperature. Remove the contents from the furnace and grind them in a mortar for 30 minutes to obtain the pre-calcined powder.

[0084] (3) Secondary ball milling

[0085] The pre-calcined powder was placed in a nylon can, and milled using zirconium balls as grinding media and anhydrous ethanol as the milling medium (anhydrous ethanol to pre-calcined powder mass ratio of 1:1.2) at 250 rpm for 72 hours. The zirconium balls were then separated, and the pre-calcined powder was dried in a drying oven at 80°C for 15 hours. After grinding in a mortar for 10 minutes and passing through a 200-mesh sieve, 0.05Pb(Mn) could be obtained. 1 / 3 Sb 2 / 3 )O3-0.5PbZrO3-0.45PbTiO3 (PMS-PZT) powder.

[0086] 2. Preparation of PMS-PZT textured piezoelectric ceramic green bodies:

[0087] (1) Preparation of slurry

[0088] The raw materials were prepared by adding 0.125 wt% CuO and an excess of 1.5 wt% PbO, 0.8130 g of dispersant (castor oil), 2.8456 g of organic binder (PVB), 0.8130 g of plasticizer (butyl phthalate and polyethylene glycol), and 10.1629 g of solvent (a mixture of ethanol and xylene in a 1:1 mass ratio) to PMS-PZT powder. The mixture was placed in a nylon container and ball-milled for 24 hours at 250 rpm using zirconium balls. The zirconium balls were then separated through a sieve, and the slurry was poured into a beaker. 2% BZT seed crystal template was added, and the slurry was further prepared by magnetic stirring at 300 rpm.

[0089] (2) Casting

[0090] In the tape casting process, to obtain ceramic film tapes with uniform thickness, dense structure, and good green strength, this invention employs a precisely controlled scraper device to pull the substrate at a stable speed of 0.5 cm / s, while simultaneously setting the blade height precisely to 200 micrometers, thus casting PMS-PZT ceramic film tapes. The front and rear temperatures of the tape casting machine are 35°C and 45°C, respectively.

[0091] (3) Stacking

[0092] The PMS-PZT ceramic film strip was cut into 25mm*25mm squares, stacked in a mold, and hot-pressed at 80°C for 5 minutes. After the mold temperature dropped to room temperature, sample sheets were obtained. The sample sheets were stacked to 2mm and then heated to 550°C to remove the adhesive and organic matter, thus obtaining the PMS-PZT textured piezoelectric ceramic green body.

[0093] 3. Preparation of high-power PMS-PZT textured piezoelectric ceramics

[0094] (1) Tableting

[0095] The PMS-PZT textured piezoelectric ceramic green body was subjected to cold isostatic pressing at 200 MPa for 15 min.

[0096] (2) Pressureless closed sintering

[0097] The PMS-PZT textured piezoelectric ceramic green body after cold isostatic pressing is embedded in homogeneous powder, placed on a zirconia plate, and then placed in an alumina sealed crucible. The temperature is increased to 1200℃ at a heating rate of 3℃ / min, and sintered for 5 hours. After cooling to room temperature, the sintered PMS-PZT textured piezoelectric ceramic is obtained, which is denoted as T-PMS.

[0098] (3) Polishing

[0099] The upper and lower surfaces of the sintered PMS-PZT textured piezoelectric ceramic were polished with 600-grit sandpaper, and then polished with metallographic sandpaper to a thickness of 1.2 mm. Afterward, they were ultrasonically cleaned with deionized water and ethanol, and then dried. The sintered textured piezoelectric ceramic sample was cut into 31 piezoelectric vibration modes (the ratio of its length, width and height is 12:3:1).

[0100] (4) Silver-plated electrode

[0101] Silver paste is evenly coated onto the two polished ceramic surfaces and placed in a resistance furnace. The furnace is kept at 600℃ for 30 minutes and then allowed to cool naturally to room temperature to obtain piezoelectric ceramics with silver electrodes.

[0102] (5) Polarization

[0103] The silver-plated piezoelectric ceramic was placed in silicone oil and polarized along the thickness direction using a DC or AC electric field. The polarization temperature was 150℃, the polarization voltage was 30kV / cm, and the polarization voltage was held for 30min to obtain the PMS-PZT textured piezoelectric ceramic, which was marked as T-PMS-PZT.

[0104] Comparative Example 1

[0105] The difference between Comparative Example 1 and Example 1 is as follows:

[0106] In the process of preparing PMS-PZT piezoelectric ceramic green body, in step S2 (1) of preparing the slurry, no BZT seed template is added. After the process is completed, ordinary slurry is obtained. Other steps are the same as in Example 1. The product obtained is PMS-PZT ordinary piezoelectric ceramic, labeled as R-PMS-PZT.

[0107] Figure 1 The images show cross-sectional scanning electron microscope (SEM) images of the ordinary PMS-PZT piezoelectric ceramic (R-PMS-PZT) prepared in Comparative Example 1 and the textured piezoelectric ceramic (T-PMS-PZT) prepared in Example 1 of this invention. As can be seen from the figures, the PMS-PZT textured piezoelectric ceramic prepared in Example 1 of this invention has uniform grain size and a dense structure. Compared with the equiaxed grains observed in the non-textured piezoelectric ceramic (i.e., ordinary piezoelectric ceramic) prepared in Comparative Example 1 of this invention, the textured piezoelectric ceramic exhibits a highly uniform grain structure due to the template-induced preferred orientation growth of the matrix grains. <001> The orientation of the grains is significantly larger than that of non-textured piezoelectric ceramics.

[0108] Figure 2 The XRD patterns of the ordinary PMS-PZT piezoelectric ceramic (R-PMS-PZT) prepared in Comparative Example 1 and the textured piezoelectric ceramic (T-PMS-PZT) prepared in Example 1 are shown in the figure. As can be seen from the figure, all samples exhibit a single perovskite structure, with no second phase detected within the test range. Furthermore, the phase structures are all near the morphotropic phase boundary (MPB), with the trigonal phase being dominant. The diffraction peaks of the textured piezoelectric ceramic are mainly (001) and (002), indicating a high degree of texture. Grain epitaxy using a template successfully achieved grain growth along the grain boundaries. <001> The orientation is preferentially arranged, which significantly enhances the anisotropic properties of the material.

[0109] Figure 3 This graph shows the dielectric constant of the ordinary PMS-PZT piezoelectric ceramic (R-PMS-PZT) prepared in Comparative Example 1 and the textured piezoelectric ceramic (T-PMS-PZT) prepared in Example 1 as a function of temperature. As can be seen from the graph, the textured piezoelectric ceramic prepared in Example 1 has a high Curie temperature (299ºC) and low dielectric loss (0.34%), making it suitable for use in high-power devices.

[0110] Figure 4The figures show the hysteresis loops of the ordinary PMS-PZT piezoelectric ceramic (R-PMS-PZT) prepared in Comparative Example 1 and the textured piezoelectric ceramic (T-PMS-PZT) prepared in Example 1. As can be seen from the figure, at an electric field of 40 kV / cm, the coercive field of the ordinary PMS-PZT ceramic is 11.5 kV / cm, while that of the textured piezoelectric ceramic is 12.8 kV / cm. The larger coercive field can improve the withstand voltage threshold of the piezoelectric ceramic, making it suitable for high-power device applications.

[0111] Figure 5 The impedance diagram and phase angle of the textured piezoelectric ceramic (T-PMS-PZT) prepared in Example 1 of this invention are shown in the figure. As can be seen from the figure, calculations can yield... Q m With a power output of up to 694, it boasts excellent high-power performance.

[0112] Figure 6 The figure shows the vibration velocity of the textured piezoelectric ceramic (T-PMS-PZT) prepared in Example 1 of this invention. As can be seen from the figure, the vibration velocity is 1.8 m / s under an AC electric field of 100 V / mm.

[0113] Example 2

[0114] A method for preparing textured piezoelectric ceramics includes the following steps:

[0115] S1: Preparation of 0.05Pb(Mn) 1 / 3 Sb 2 / 3 The method for producing O3-0.5PbZrO3-0.45PbTiO3 powder is as follows:

[0116] (1) Ingredients

[0117] According to 0.05Pb(Mn 1 / 3 Sb 2 / 3 The raw materials were prepared by stoichiometric ratio of Pb3O3-0.5PbZrO3-0.45PbTiO3 (PMS-PZT). 68.7915g of Pb3O4 (99% purity), 0.4362g of MnO2 (99% purity), 18.6757g of ZrO2 (99.9% purity), 10.7245g of TiO2 (99.9% purity), and 1.4265g of Sb2O3 (99% purity) were weighed out as raw materials. All raw materials were mixed thoroughly and placed in a nylon container. Using zirconium balls as grinding media and anhydrous ethanol as the milling medium, the mixture was ball-milled for 18 hours to obtain a raw material mixture. The zirconium balls were separated, and the raw material mixture was dried at 100℃ for 24 hours. The mixture was then ground in a mortar and pestle and passed through a 200-mesh sieve.

[0118] (2) Pre-firing

[0119] The raw material mixture after passing through a 200-mesh sieve in step (1) is placed in an alumina crucible, compacted with an agate rod, covered, and placed in a resistance furnace. It is pre-fired at 850°C for 10 hours at a heating rate of 10°C / min. After cooling naturally to room temperature, it is removed from the furnace and ground with a mortar and pestle to obtain pre-fired powder.

[0120] (4) Secondary ball milling

[0121] The pre-calcined powder was placed in a nylon can, and milled for 12 hours at 300 rpm using zirconium balls as grinding media and anhydrous ethanol as the milling medium. The zirconium balls were then separated, and the pre-calcined powder was dried at 100°C for 24 hours. The powder was then ground in a mortar and pestle and passed through an 80-mesh sieve to obtain 0.05Pb(Mn)2. 1 / 3 Sb 2 / 3 O3-0.5PbZrO3-0.45PbTiO3 powder, i.e. PMS-PZT powder;

[0122] S2, Preparation of 0.05Pb(Mn) 1 / 3 Sb 2 / 3 O3-0.5PbZrO3-0.45PbTiO3 textured piezoelectric ceramic green body:

[0123] (1) Preparation of slurry

[0124] Prepared using a plate-shaped BZT seed template via template grain growth (TGG) <001> Oriented PMS-PZT textured piezoelectric ceramics. Specifically, CuO, a sintering aid, is added to PMS-PZT powder, followed by a certain amount of PbO. Since lead volatilizes during sintering, a certain amount of PbO is added here. Dispersant (castor oil), organic binder (PVB), plasticizer (butyl phthalate and polyethylene glycol), and solvent (ethanol and xylene) are also added, followed by ball milling. Subsequently, a BZT seed template is added using magnetic stirring to prepare a slurry. The amounts of CuO, PbO, dispersant, organic binder, plasticizer, and solvent added are 0.05%, 1.0%, 0.5%, 2.0%, 0.5%, and 8% of the PMS-PZT powder mass, respectively; the amount of BZT seed template added is 1% of the PMS-PZT powder mass.

[0125] (2) Casting and stacking

[0126] In the tape casting process, to obtain ceramic film strips with uniform thickness, dense structure, and good green strength, this invention employs a precisely controlled scraper device to pull the substrate at a stable speed of 0.5 cm / s, while simultaneously setting the blade height precisely to 200 micrometers. The light gray film strip obtained through tape casting is cut into squares, stacked, and then hot-pressed at 80°C. The hot-pressed green body is heated to 550°C to remove the binder and organic matter, yielding a PMS-PZT textured piezoelectric ceramic green body.

[0127] S3. Fabrication of high-power PMS-PZT textured piezoelectric ceramics

[0128] (1) Cold isostatic pressing

[0129] The PMS-PZT textured piezoelectric ceramic green body was subjected to cold isostatic pressing at a pressure of 300 MPa for 15-20 min.

[0130] (2) Pressureless closed sintering

[0131] The PMS-PZT textured piezoelectric ceramic green body after cold isostatic pressing is embedded in homogeneous powder, placed on a zirconia plate, and then placed in an alumina sealed sagger. The temperature is raised to 1150℃ at a heating rate of 5℃ / min, sintered for 10 hours, and then naturally cooled to room temperature in the furnace to obtain the fired piezoelectric ceramic.

[0132] (3) Polishing

[0133] The upper and lower surfaces of the sintered piezoelectric ceramic were polished with 2000-grit sandpaper, and then polished with metallographic sandpaper to a thickness of 0.8 mm. Afterwards, they were ultrasonically cleaned with deionized water and ethanol, and then dried.

[0134] (4) Silver-plated electrode

[0135] The silver paste is evenly coated on the two polished surfaces of the ceramic, placed in a resistance furnace, and kept at 500℃ for 60 minutes. The ceramic is then allowed to cool naturally to room temperature to obtain a piezoelectric ceramic with silver electrode plating.

[0136] (5) Polarization

[0137] The silver-plated piezoelectric ceramic was immersed in silicone oil and polarized along its thickness using a DC or AC electric field. The polarization temperature was 90℃, the polarization voltage was 10 kV / cm, and the polarization voltage was maintained for 30 min, yielding a product with the chemical formula 0.05Pb(Mn). 1 / 3 Sb 2 / 3 Textured piezoelectric ceramics of O3-0.5PbZrO3-0.45PbTiO3.

[0138] The crystallographic orientation of the textured piezoelectric ceramic prepared in this embodiment is as follows: <001> Orientation, the Curie temperature of the textured piezoelectric ceramic is 299°C, and the piezoelectric constant is... d 33 The mechanical quality factor is 700 pC / N. Q m For 690, the stubborn field E C The vibration voltage is 12.8 kV / cm, and the vibration velocity is 1.8 m / s.

[0139] Example 3

[0140] A method for preparing textured piezoelectric ceramics includes the following steps:

[0141] S1: Preparation of 0.05Pb(Mn) 1 / 3 Sb 2 / 3 The method for producing O3-0.5PbZrO3-0.45PbTiO3 powder is as follows:

[0142] (1) Ingredients

[0143] According to 0.05Pb(Mn 1 / 3 Sb 2 / 3 The raw materials were prepared by stoichiometric ratio of Pb3O3-0.5PbZrO3-0.45PbTiO3 (PMS-PZT). 68.7915g of Pb3O4 (99% purity), 0.4362g of MnO2 (99% purity), 18.6757g of ZrO2 (99.9% purity), 10.7245g of TiO2 (99.9% purity), and 1.4265g of Sb2O3 (99% purity) were weighed out as raw materials. All raw materials were mixed thoroughly and placed in a nylon container. Using zirconium balls as grinding media and anhydrous ethanol as the milling medium, the mixture was ball-milled for 30 hours to obtain a raw material mixture. The zirconium balls were separated, and the raw material mixture was dried at 80℃ for 20 hours. It was then ground in a mortar and pestle and passed through a 100-mesh sieve.

[0144] (2) Pre-firing

[0145] The raw material mixture after passing through a 100-mesh sieve in step (1) is placed in an alumina crucible, compacted with an agate rod, covered, and placed in a resistance furnace. It is pre-fired at 800°C for 4 hours at a heating rate of 5°C / min. After cooling naturally to room temperature, it is removed from the furnace and ground with a mortar and pestle to obtain pre-fired powder.

[0146] (4) Secondary ball milling

[0147] The pre-calcined powder was placed in a nylon can, and milled for 50 hours at 300 rpm using zirconium balls as grinding media and anhydrous ethanol as the milling medium. The zirconium balls were then separated, and the pre-calcined powder was dried at 90°C for 20 hours. The powder was then ground in a mortar and pestle and passed through a 100-mesh sieve to obtain 0.05Pb(Mn)2.1 / 3 Sb 2 / 3 O3-0.5PbZrO3-0.45PbTiO3 powder, i.e. PMS-PZT powder;

[0148] S2, Preparation of 0.05Pb(Mn) 1 / 3 Sb 2 / 3 O3-0.5PbZrO3-0.45PbTiO3 textured piezoelectric ceramic green body:

[0149] (1) Preparation of slurry

[0150] Prepared using a plate-shaped BZT seed template via template grain growth (TGG) <001> Oriented PMS-PZT textured piezoelectric ceramics. Specifically, CuO, a sintering aid, is added to PMS-PZT powder, followed by a certain amount of PbO. Since lead volatilizes during sintering, a certain amount of PbO is added here. Dispersant (castor oil), organic binder (PVB), plasticizer (butyl phthalate and polyethylene glycol), and solvent (ethanol and xylene) are also added, followed by ball milling. Subsequently, a BZT seed template is added using magnetic stirring to prepare a slurry. The amounts of CuO, PbO, dispersant, organic binder, plasticizer, and solvent added are 0.3%, 3.0%, 1.5%, 4.0%, 1.5%, and 15% of the PMS-PZT powder mass, respectively; the amount of BZT seed template added is 5% of the PMS-PZT powder mass.

[0151] (2) Casting and stacking

[0152] In the tape casting process, to obtain ceramic film strips with uniform thickness, dense structure, and good green strength, this invention employs a precisely controlled scraper device to pull the substrate at a stable speed of 0.5 cm / s, while simultaneously setting the blade height precisely to 200 micrometers. The light gray film strip obtained through tape casting is cut into squares, stacked, and then hot-pressed at 80°C. The hot-pressed green body is heated to 550°C to remove the binder and organic matter, yielding a PMS-PZT textured piezoelectric ceramic green body.

[0153] S3. Fabrication of high-power PMS-PZT textured piezoelectric ceramics

[0154] (1) Cold isostatic pressing

[0155] The PMS-PZT textured piezoelectric ceramic green body was subjected to cold isostatic pressing at 250 MPa for 18 min.

[0156] (2) Pressureless closed sintering

[0157] The PMS-PZT textured piezoelectric ceramic green body after cold isostatic pressing is embedded in homogeneous powder, placed on a zirconia plate, and then placed in an alumina sealed sagger. The temperature is raised to 1300℃ at a heating rate of 5℃ / min, sintered for 8 hours, and then naturally cooled to room temperature in the furnace to obtain the fired piezoelectric ceramic.

[0158] (3) Polishing

[0159] The upper and lower surfaces of the sintered piezoelectric ceramic were polished with 1000-grit sandpaper, and then polished with metallographic sandpaper to a thickness of 1.0 mm. After that, they were ultrasonically cleaned with deionized water and ethanol, and then dried.

[0160] (4) Silver-plated electrode

[0161] The silver paste is evenly coated on the two polished surfaces of the ceramic, placed in a resistance furnace, and kept at 850℃ for 5 minutes. The ceramic is then allowed to cool naturally to room temperature to obtain a piezoelectric ceramic with silver electrode plating.

[0162] (5) Polarization

[0163] The silver-plated piezoelectric ceramic was immersed in silicone oil and polarized along its thickness using a DC or AC electric field. The polarization temperature was 100℃, the polarization voltage was 3kV / cm, and the polarization voltage was maintained for 30 min, yielding a product with the chemical formula 0.05Pb(Mn). 1 / 3 Sb 2 / 3 Textured piezoelectric ceramics of O3-0.5PbZrO3-0.45PbTiO3.

[0164] The crystallographic orientation of the textured piezoelectric ceramic prepared in this embodiment is as follows: <001> Orientation, the Curie temperature of the textured piezoelectric ceramic is 299°C, and the piezoelectric constant is... d 33 The mechanical quality factor is 750 pC / N. Q m For 720, the stubborn field E C The vibration voltage is 12.8 kV / cm, and the vibration velocity is 1.8 m / s.

[0165] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A method of fabricating a textured piezoelectric ceramic, characterized by, Includes the following steps: S1: Pb3O4, MnO2, ZrO2, TiO2, and Sb2O3 are mixed according to a ratio of 0.05Pb(MnO2) / 2. 1 / 3 Sb 2 / 3 After mixing O3-0.5PbZrO3-0.45PbTiO3 in a stoichiometric ratio, the mixture is subjected to ball milling, drying, grinding, and sieving once to obtain a raw material mixture. The raw material mixture is then pre-calcined to obtain pre-calcined powder. The pre-calcined powder is then subjected to ball milling, drying, grinding, and sieving twice to obtain PMS-PZT powder. S2: CuO, PbO, dispersant, organic binder, plasticizer and solvent are added to the PMS-PZT powder, and the mixture is ball-milled three times. After the milling is completed, three crystal templates (Ba,Zr)TiO are added to obtain a slurry. The slurry is then subjected to tape casting, stacking and hot pressing treatments in sequence to obtain a PMS-PZT textured piezoelectric ceramic green body. S3: The PMS-PZT textured piezoelectric ceramic green body is subjected to cold isostatic pressing, sintering, polishing, silver plating and polarization treatment in sequence to obtain the textured piezoelectric ceramic. In step S1, the time for the first ball milling is 18~48 hours; the time for the second ball milling is 12~72 hours. In step S2, the amount of CuO and PbO added accounts for 0.05%~0.3% and 1.0%~3.0% of the mass of PMS-PZT powder, respectively; the amount of the (Ba,Zr)TiO3 seed template added is 1%~5% of the PMS-PZT powder. In step S3, the pressure of cold isostatic pressing is 200~300MPa, and the time is 15~20min; The sintering process is as follows: the temperature is increased to 1100-1300℃ at a heating rate of 2-5℃ / min, and sintered for 5-10 hours.

2. The method of claim 1, wherein the piezoelectric ceramic is textured. Zirconium balls were used as grinding balls and anhydrous ethanol was used as the grinding medium in both the primary and secondary ball milling processes.

3. The method of claim 1, wherein the piezoelectric ceramic is textured. The temperature for both primary and secondary drying is 80~100℃, and the time is 12~24h; the mesh size of the sieve is 80~200 mesh for both primary and secondary sieving.

4. The method of claim 1, wherein the piezoelectric ceramic is textured. The pre-firing process specifically involves pre-firing at a temperature of 750℃~850℃ for 2~5 hours at a heating rate of 2~10℃ / min.

5. The method of claim 1, wherein the piezoelectric ceramic is textured. In step S2, the amounts of dispersant, organic binder, plasticizer, and solvent added account for 0.5%~1.5%, 2.0%~4.0%, 0.5%~1.5%, and 8%~15% of the mass of PMS-PZT powder, respectively.

6. The method of claim 1, wherein the piezoelectric ceramic is textured. In step S3, the polishing process involves using 600-2000 grit sandpaper.

7. The method of claim 1, wherein the piezoelectric ceramic is textured. In step S3, the silver plating specifically involves: uniformly coating the polished surface with silver paste and placing it in a resistance furnace, holding it at a temperature of 500~850℃ for 5~60 minutes, and then allowing it to cool naturally to room temperature; in the polarization treatment, the polarization temperature is 90~150℃, the polarization voltage is 10~50kV / cm, and the polarization voltage holding time is 10~60 minutes.

8. A textured piezoelectric ceramic, characterized in that, The textured piezoelectric ceramic is prepared by the method described in any one of claims 1 to 7; the crystallographic orientation of the textured piezoelectric ceramic is as follows: <001> Orientation, the Curie temperature of the textured piezoelectric ceramic is 299°C, and the piezoelectric constant is... d 33 Mechanical quality factor: 700~750 pC / N Q m The range is 690~720, with a strong field. E C The vibration voltage is 12.8 kV / cm, and the vibration velocity is 1.8 m / s.

9. The application of the textured piezoelectric ceramic as described in claim 8 in a sonar buoy.

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