High-performance PSN-PMN-PZ-PT quaternary textured piezoelectric ceramic material and preparation method thereof

Abstract

This invention discloses a high-performance PSN-PMN-PZ-PT quaternary textured piezoelectric ceramic material and its preparation method, with the chemical formula xPb(Sc) 1 / 2 Nb 1 / 2 O3-(1-x-y-z)Pb(Mg) 1 / 3Nb 2 / 3 )O3-yPbZrO3-zPbTiO3-aEu2O3-bwt%BaTiO3, where x, y, z, and a all represent mole fractions, 0

Description

Technical Field

[0001] This invention belongs to the field of piezoelectric ceramic technology, specifically relating to a high-performance PSN-PMN-PZ-PT quaternary textured piezoelectric ceramic material and its preparation method. Background Technology

[0002] Piezoelectric ceramics, as important functional materials for electronic information, can realize the conversion between electrical energy and mechanical energy, and are widely used in various device fields, including sonar, piezoelectric actuators, medical ultrasound transducers, and energy harvesters. Among them, lead-based piezoelectric ceramics have long dominated the piezoelectric ceramic market due to their advantages such as low manufacturing cost, ease of processing, and high product reproducibility. However, research has found that the Curie temperature of piezoelectric ceramics is often negatively correlated with their piezoelectric properties; that is, the larger the piezoelectric coefficient, the lower the Curie temperature. With the further development of electronic devices, higher requirements are being placed on the performance of piezoelectric ceramics.

[0003] Compared to ceramics with randomly oriented grains, textured ceramics with grains oriented along the

[001] axis can significantly improve piezoelectric properties while maintaining the Curie temperature, making them a current research hotspot. Researchers have conducted extensive studies on the development of binary and ternary textured ceramics, resulting in significant improvements in the performance of lead-based textured ceramics. Furthermore, it has been found that ternary textured ceramics outperform binary textured ceramics. Therefore, developing a new generation of quaternary textured ceramics is an effective means to obtain ceramics that combine high Curie temperature and high piezoelectric properties.

[0004] Engineering domain theory indicates that when the crystal structure is trigonal, the "4R" engineering domains formed when polarized along the

[001] direction have higher piezoelectric properties than those polarized along other directions. Therefore, the composition of

[001] oriented textured ceramics must be close to the trigonal phase region at its quasi-isomorphic phase boundary. However, due to the complexity of the composition, the quasi-isomorphic phase boundary composition is already quite complex for ternary systems. In quaternary systems, where four component variables exist simultaneously, finding the quasi-isomorphic phase boundary composition becomes even more difficult.

[0005] Currently, the domain sizes of lead-based textured ceramics are relatively small. However, some experimental studies have shown that there may be a relationship between domain size and macroscopic piezoelectric properties, where larger ferroelectric domain sizes correlate with higher piezoelectricity. Therefore, researching and developing a novel quaternary textured piezoelectric ceramic composition with large-sized domains is of great significance for obtaining high Curie temperatures and high piezoelectric properties, in order to meet the application requirements of next-generation electronic devices. Summary of the Invention

[0006] To address the aforementioned technical problems, this invention aims to provide a high-performance PSN-PMN-PZ-PT quaternary textured piezoelectric ceramic material and its preparation method, overcoming the current problem of mutual constraint between the piezoelectric properties and Curie temperature of lead-based piezoelectric ceramics. This invention, through the design of a quaternary textured ceramic composition and combined with a specific preparation process, obtains a

[001] -oriented lead-based textured piezoelectric ceramic material with high piezoelectric properties and high Curie temperature. The method is controllable, and the piezoelectric constant of the prepared ceramic material is 2.2 times that of randomly oriented ceramics, exhibiting excellent performance.

[0007] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0008] A high-performance PSN-PMN-PZ-PT quaternary textured piezoelectric ceramic material with the chemical formula xPb(Sc) 1 / 2Nb 1 / 2 O3-(1-xyz)Pb(Mg) 1 / 3 Nb 2 / 3 )O3-yPbZrO3-zPbTiO3-aEu2O3-bwt%BaTiO3, where x, y, z, and a all represent mole fractions, 0 <x≤0.15,0.1≤y≤0.25,0.32≤z≤0.4,0.005≤a≤0.02,1≤b≤5。

[0009] As a limitation of the electroceramic material of the present invention, the structure of the ceramic material is a perovskite structure.

[0010] In the piezoelectric ceramic material formulation of this invention, xPb(Sc) 1 / 2 Nb 1 / 2 O3-(1-xyz)Pb(Mg) 1 / 3 Nb 2 / 3 O3-yPbZrO3-zPbTiO3 serves as the matrix material. The complexity of the B-site elements enhances the internal disorder of the system, thereby weakening the long-range ferroelectric order. This is beneficial for obtaining a flat free energy curve, thus improving piezoelectric properties. Simultaneously, the high Curie temperature PSN, PZ, and PT components within the system ensure that the final textured ceramic exhibits a high Curie temperature. 3+ As a doping element, it generates a large number of local heterostructures in the material, thereby improving the electrical properties of the material;

[001] Oriented BaTiO3 is used as a template to induce the orientation growth of ceramic grains in order to obtain textured ceramics with high orientation.

[0011] This invention also provides a method for preparing a high-performance PSN-PMN-PZ-PT quaternary textured piezoelectric ceramic material, which is carried out in the following order:

[0012] S1. Prepare the ingredients according to the stoichiometric ratio, and ball mill using anhydrous ethanol as the ball milling medium. After ball milling, dry the powder and press it into... The block was pre-fired, and the pre-fired block was ball-milled again for 12-24 hours to obtain perovskite phase powder, denoted as A;

[0013] S2. Mix A with solvent and trioleic acid glyceride, and ball mill for 12-24 hours to obtain B;

[0014] S3. Add polyvinyl butyral and dioctyl phthalate to B, mix and ball mill for 12-24 hours, then add BaTiO3 template and ball mill at low speed for 0.5-1.5 hours to obtain C;

[0015] S4. Degas C, then cast it to obtain a film. Cut, stack, and hot press the obtained film to obtain a ceramic preform. Then, isostatically press the ceramic preform at 150-230MPa for 2 minutes to obtain D.

[0016] S5. After holding the body at 550-650℃ for 2 hours to remove the glue, the body is then isostatically pressed at 150-230MPa for 1 minute to obtain a dense ceramic body, E.

[0017] S6. Place E into a muffle furnace for sintering. The sintering process is carried out in an oxygen atmosphere. The temperature is increased to 800℃ at a heating rate of 5℃ / min and held for 1 hour. Then the temperature is increased to 1200℃ at a heating rate of 8℃ / min and held for 1 hour. Then the temperature is decreased to 1150℃ at a heating rate of 8℃ / min and held for 20 hours. Finally, the temperature is decreased to 800℃ and held for 1 hour. The furnace is then cooled to room temperature to obtain a textured ceramic material with

[001] orientation, denoted as F.

[0018] E was sintered in a muffle furnace under an oxygen atmosphere to promote densification and grain growth, thereby achieving high texture. The temperature was increased to 800℃ at a rate of 5℃ / min and held for 1 hour. This process allowed the liquid phase film to fully diffuse within the matrix grains, which is beneficial for the subsequent growth of textured grains. The temperature was then increased to 1200℃ at a rate of 8℃ / min and held for 1 hour, followed by a decrease to 1150℃ at a rate of 8℃ / min and held for 20 hours. Rapid heating avoided the growth of randomly oriented small grains, while the longer holding time at 1150℃ allowed for sufficient growth of oriented grains, resulting in larger grains. Finally, the temperature was decreased to 800℃ and held for 1 hour to remove excess Pb. 2+ To avoid segregation at grain boundaries, a textured ceramic material with

[001] orientation is obtained, which further ensures the large size of its ferroelectric domains;

[0019] S7. Polish the two sides of F perpendicular to the

[001] orientation until smooth, then uniformly coat with silver electrodes, and finally polarize in silicone oil. After polarization, a piezoelectric ceramic material is obtained.

[0020] As a limitation of the preparation method of the present invention, in step S1, the pre-firing temperature is 750-820℃ and the pre-firing time is 2h.

[0021] As a second limitation of the preparation method of the present invention, in step S2, the solvent is a mixture of anhydrous ethanol and butanone in a mass ratio of 1:2, and the mass ratio of the solvent, trioleic acid glyceride and A is 54:3:100.

[0022] In this invention, the mass ratio of solvent, trioleic acid glyceride, and A affects the uniformity and drying rate of the film obtained by casting, and thus affects the density of the textured ceramic.

[0023] As a third limitation of the preparation method of the present invention, in step S3, the mass ratio of polyvinyl butyral, dioctyl phthalate and A is 2:2:25.

[0024] In this invention, the mass ratio of polyvinyl butyral, dioctyl phthalate, and B affects the viscosity of C, which in turn affects the orientation of the template in the casting process, and also affects the porosity of the final ceramic material, thus affecting the performance of the textured ceramic.

[0025] As a fourth limitation of the preparation method of the present invention, in step S3, the first ball milling speed is 280-350 r / min, and the low-speed ball milling speed is 150-250 r / min.

[0026] As a fifth limitation of the preparation method of the present invention, in step S2, the ball milling speed is 280-350 r / min.

[0027] The present invention also has a limitation: in step S7, the polarization temperature is 150°C, the polarization voltage is 30 kV / cm, and the polarization time is 15 min.

[0028] In this invention, the polarization process is carried out at high temperature. The polarization parameters affect the reorientation of electric domains in the sample, and thus affect the electrical properties of the textured ceramic.

[0029] The above-mentioned technical solution of the present invention is a whole in which each step is closely related and mutually influential, and together they determine the morphological characteristics and performance of the product.

[0030] The above technical solution has the following advantages or beneficial effects:

[0031] 1. This invention improves piezoelectric performance without significantly sacrificing Curie temperature through component ratio design, obtaining a PSN-PMN-PZ-PT quaternary textured ceramic with high texture along the

[001] orientation. This overcomes the problem of mutual restriction between piezoelectric performance and Curie temperature in current lead-based piezoelectric ceramics, and obtains a

[001] -oriented lead-based textured piezoelectric ceramic material with both high Curie temperature and high piezoelectric performance. The process of this method is controllable.

[0032] 2. This invention uses a multi-stage sintering process design to allow oriented grains to grow fully, resulting in textured ceramics with large-size electric domains.

[0033] 3. The piezoelectric ceramic material prepared by this invention has a texture degree of over 98%, and its piezoelectric constant, Curie temperature and coercive field are as high as 1275 pC / N, 241℃ and 7.15 kV / cm, respectively. Among them, the piezoelectric constant is 2.2 times that of randomly oriented ceramics.

[0034] 4. The preparation method of the present invention is easy to control, and the prepared product has wide adaptability and is suitable for industrial application. Attached Figure Description

[0035] Figure 1 The XRD patterns of the ceramic materials prepared in Example 2 and Comparative Examples 1, 2 and 3 of this invention are shown below.

[0036] Figure 2 These are cross-sectional scan images of the ceramic materials prepared in Example 2, Comparative Examples 1 and 3 of the present invention;

[0037] Figure 3 This is a comparison of the dielectric temperature spectra of the ceramic materials prepared in Example 2 of the present invention with those prepared in Comparative Examples 1 and 2.

[0038] Figure 4 This is a comparison diagram of the piezoelectric properties of the ceramic materials prepared in Example 2 of the present invention with those prepared in Comparative Examples 1, 2, and 3.

[0039] Figure 5 This is a comparison of PFM images of the ceramic materials prepared in Example 2 and Comparative Example 3 of the present invention. Detailed Implementation

[0040] The following embodiments are merely some, not all, of the embodiments of the present invention. Therefore, the detailed descriptions of the embodiments provided below are not intended to limit the scope of the claimed invention, but merely to illustrate selected embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without inventive effort are within the scope of protection of the present invention.

[0041] In this invention, unless otherwise specified, all equipment and raw materials are commercially available or commonly used in the industry. The methods described in the following embodiments are conventional methods in the art, unless otherwise specified.

[0042] Example

[0043] Example 1: A method for preparing a high-performance PSN-PMN-PZ-PT quaternary textured piezoelectric ceramic material. The chemical formula of the material prepared in this example is:

[0044] 0.03Pb(Sc 1 / 2 Nb 1 / 2 O3-0.42Pb(Mg) 1 / 3 Nb 2 / 3 The specific preparation process is as follows: O3-0.25PbZrO3-0.32PbTiO3-0.02Eu2O3-5wt%BaTiO3.

[0045] S1. Prepare the ingredients according to the stoichiometric ratio, and ball mill using anhydrous ethanol as the ball milling medium. After ball milling, dry the powder and press it into... The block was pre-fired at 750℃ for 2 hours. After pre-firing, the block was ball-milled again for 12 hours to obtain perovskite phase powder, denoted as A.

[0046] S2. Mix A with solvent and trioleic acid glyceride in a mass ratio of 100:54:3 and ball mill at 280 r / min for 12 h to obtain B;

[0047] S3. Polyvinyl butyral and dioctyl phthalate were added to B, with a mass ratio of polyvinyl butyral and dioctyl phthalate to A of 2:2:25. After mixing, the mixture was ball-milled for the first time with the following parameters: ball-milling time of 12 hours and ball-milling speed of 350 r / min. Then, a BaTiO3 template was added and ball-milled at low speed for 1 hour with a ball-milling speed of 250 r / min to obtain C.

[0048] S4. Degas C, then cast it to obtain a film. Cut, stack, and hot press the obtained film to obtain a ceramic preform. Then, isostatically press the ceramic preform at 200MPa for 2 minutes to obtain D.

[0049] S5. After holding the ceramic body at 600℃ for 2 hours to remove the glue, the body is then isostatically pressed at 230MPa for 1 minute to obtain a dense ceramic body, which is E.

[0050] S6. Place E into a muffle furnace for sintering. The sintering process is carried out in an oxygen atmosphere. The temperature is increased to 800℃ at a heating rate of 5℃ / min and held for 1 hour. Then the temperature is increased to 1200℃ at a heating rate of 8℃ / min and held for 1 hour. Then the temperature is decreased to 1150℃ at a heating rate of 8℃ / min and held for 20 hours. Finally, the temperature is decreased to 800℃ and held for 1 hour. The furnace is then cooled to room temperature to obtain a textured ceramic material with

[001] orientation, denoted as F.

[0051] S7. Polish the two sides of F perpendicular to the

[001] orientation until smooth, then uniformly coat with silver electrodes, and finally polarize in silicone oil. The polarization temperature is 150℃, the polarization voltage is 30kV / cm, and the polarization time is 15min. After polarization, the piezoelectric ceramic material is obtained.

[0052] Example 2: A method for preparing a high-performance PSN-PMN-PZ-PT quaternary textured piezoelectric ceramic material. The chemical formula of the material prepared in this example is:

[0053] 0.07Pb(Sc 1 / 2 Nb 1 / 2 O3-0.35Pb(Mg) 1 / 3 Nb 2 / 3 The specific preparation process is as follows: O3-0.2PbZrO3-0.38PbTiO3-0.01Eu2O3-1wt%BaTiO3.

[0054] S1. Prepare the ingredients according to the stoichiometric ratio, and ball mill using anhydrous ethanol as the ball milling medium. After ball milling, dry the powder and press it into... The block was pre-fired at 800℃ for 2 hours. After pre-firing, the block was ball-milled again for 20 hours to obtain perovskite phase powder, denoted as A.

[0055] S2. Mix A with solvent and trioleic acid glyceride in a mass ratio of 100:54:3 and ball mill at 300 r / min for 18 h to obtain B;

[0056] S3. Polyvinyl butyral and dioctyl phthalate were added to B, with a mass ratio of polyvinyl butyral and dioctyl phthalate to A of 2:2:25. After mixing, the mixture was ball-milled for the first time with the following parameters: ball-milling time of 20 h and ball-milling speed of 300 r / min. Then, a BaTiO3 template was added and ball-milled at low speed for 0.5 h with a ball-milling speed of 200 r / min to obtain C.

[0057] S4. Debubbling C is then performed, followed by casting to obtain a film. The obtained film is then cut, stacked, and hot-pressed to obtain a ceramic preform. The ceramic preform is then isostatically pressed at 150 MPa for 2 minutes to obtain D.

[0058] S5. After holding the ceramic body at 550℃ for 2 hours to remove the glue, the body is then isostatically pressed at 200MPa for 1 minute to obtain a dense ceramic body, which is E.

[0059] S6. Place E into a muffle furnace for sintering. The sintering process is carried out in an oxygen atmosphere. The temperature is increased to 800℃ at a heating rate of 5℃ / min and held for 1 hour. Then the temperature is increased to 1200℃ at a heating rate of 8℃ / min and held for 1 hour. Then the temperature is decreased to 1150℃ at a heating rate of 8℃ / min and held for 20 hours. Finally, the temperature is decreased to 800℃ and held for 1 hour. The furnace is then cooled to room temperature to obtain a textured ceramic material with

[001] orientation, denoted as F.

[0060] S7. Polish the two sides of F perpendicular to the

[001] orientation until smooth, then uniformly coat with silver electrodes, and finally polarize in silicone oil. The polarization temperature is 150℃, the polarization voltage is 30kV / cm, and the polarization time is 15min. After polarization, the piezoelectric ceramic material is obtained.

[0061] Example 3: A method for preparing a high-performance PSN-PMN-PZ-PT quaternary textured piezoelectric ceramic material. The chemical formula of the prepared material in this example is...

[0062] 0.15Pb(Sc 1 / 2 Nb 1 / 2 O3-0.35Pb(Mg) 1 / 3 Nb 2 / 3 The specific preparation process is as follows: O3-0.1PbZrO3-0.4PbTiO3-0.005Eu2O3-2wt%BaTiO3.

[0063] S1. Prepare the ingredients according to the stoichiometric ratio, and ball mill using anhydrous ethanol as the ball milling medium. After ball milling, dry the powder and press it into... The block was pre-fired at 820℃ for 2 hours. After pre-firing, the block was ball-milled again for 24 hours to obtain perovskite phase powder, denoted as A.

[0064] S2. Mix A with solvent and trioleic acid glyceride in a mass ratio of 100:54:3 and ball mill at 350 r / min for 24 h to obtain B;

[0065] S3. Polyvinyl butyral and dioctyl phthalate were added to B, with a mass ratio of polyvinyl butyral and dioctyl phthalate to A of 2:2:25. After mixing, the mixture was ball-milled for the first time with the following parameters: ball-milling time of 24 h and ball-milling speed of 280 r / min. Then, a BaTiO3 template was added and ball-milled at low speed with the following parameters: ball-milling time of 1.5 h and ball-milling speed of 150 r / min, to obtain C.

[0066] S4. Debubbling C is then performed, followed by casting to obtain a film. The obtained film is then cut, stacked, and hot-pressed to obtain a ceramic preform. The ceramic preform is then isostatically pressed at 230 MPa for 2 minutes to obtain D.

[0067] S5. After holding the body at 650℃ for 2 hours to remove the glue, the body is then isostatically pressed at 150MPa for 1 minute to obtain a dense ceramic body, which is E.

[0068] S6. Place E into a muffle furnace for sintering. The sintering process is carried out in an oxygen atmosphere. The temperature is increased to 800℃ at a heating rate of 5℃ / min and held for 1 hour. Then the temperature is increased to 1200℃ at a heating rate of 8℃ / min and held for 1 hour. Then the temperature is decreased to 1150℃ at a heating rate of 8℃ / min and held for 20 hours. Finally, the temperature is decreased to 800℃ and held for 1 hour. The furnace is then cooled to room temperature to obtain a textured ceramic material with

[001] orientation, denoted as F.

[0069] S7. Polish the two sides of F perpendicular to the

[001] orientation until smooth, then uniformly coat with silver electrodes, and finally polarize in silicone oil. The polarization temperature is 150℃, the polarization voltage is 30kV / cm, and the polarization time is 15min. After polarization, the piezoelectric ceramic material is obtained.

[0070] A series of performance tests were performed on the materials prepared in Examples 1-3 above, as detailed in the table below.

[0071]

[0072]

[0073] Comparative Example

[0074] To investigate the effects of Eu₂O₃ and BaTiO₃ on piezoelectric ceramic materials, different piezoelectric ceramic materials were prepared in the following comparative examples:

[0075] Comparative Example 1

[0076] The comparative sample prepared with the following chemical formula is:

[0077] 0.07Pb(Sc 1 / 2 Nb 1 / 2 O3-0.35Pb(Mg) 1 / 3 Nb 2 / 3 The specific preparation process of O3-0.2PbZrO3-0.38PbTiO3-1wt%BaTiO3 is as follows:

[0078] S1. Prepare the ingredients according to the stoichiometric ratio, and ball mill using anhydrous ethanol as the ball milling medium. After ball milling, dry the powder and press it into... The block was pre-fired at 730℃ for 2 hours. After pre-firing, the block was ball-milled again for 20 hours to obtain perovskite phase powder, denoted as A.

[0079] S2. Mix A with solvent and trioleic acid glyceride in a mass ratio of 100:54:3 and ball mill at 300 r / min for 12 h to obtain B;

[0080] S3. Polyvinyl butyral and dioctyl phthalate were added to B, with a mass ratio of polyvinyl butyral and dioctyl phthalate to A of 2:2:25. After mixing, the mixture was ball-milled for the first time with the following parameters: ball-milling time of 20 h and ball-milling speed of 300 r / min. Then, a BaTiO3 template was added and ball-milled at low speed with the following parameters: ball-milling time of 0.5 h and ball-milling speed of 200 r / min, to obtain C.

[0081] S4. Debubbling C is then performed, followed by casting to obtain a film. The obtained film is then cut, stacked, and hot-pressed to obtain a ceramic preform. The ceramic preform is then isostatically pressed at 150 MPa for 2 minutes to obtain D.

[0082] S5. After holding the ceramic body at 550℃ for 2 hours to remove the glue, the body is then isostatically pressed at 200MPa for 1 minute to obtain a dense ceramic body, which is E.

[0083] S6. Place E into a muffle furnace for sintering. The sintering process is carried out in an oxygen atmosphere. The temperature is increased to 800℃ at a heating rate of 5℃ / min and held for 1 hour. Then the temperature is increased to 1200℃ at a heating rate of 8℃ / min and held for 1 hour. Then the temperature is decreased to 1150℃ at a heating rate of 8℃ / min and held for 20 hours. Finally, the temperature is decreased to 800℃ and held for 1 hour. The furnace is then cooled to room temperature to obtain a textured ceramic material with

[001] orientation, denoted as F.

[0084] S7. Polish the two sides of F perpendicular to the

[001] orientation until smooth, then uniformly coat with silver electrodes, and finally polarize in silicone oil. The polarization temperature is 150℃, the polarization voltage is 30kV / cm, and the polarization time is 15min. After polarization, the piezoelectric ceramic material is obtained.

[0085] Comparative Example 2

[0086] The comparative sample prepared with the following chemical formula is:

[0087] 0.07Pb(Sc 1 / 2 Nb 1 / 2 O3-0.35Pb(Mg) 1 / 3 Nb 2 / 3The specific preparation process of O3-0.2PbZrO3-0.38PbTiO3-0.01Eu2O3 is as follows:

[0088] S1. Prepare the ingredients according to the stoichiometric ratio, and ball mill using anhydrous ethanol as the ball milling medium. After ball milling, dry the powder and press it into... The block was pre-fired at 730℃ for 2 hours. After pre-firing, the block was ball-milled again for 20 hours to obtain perovskite phase powder, denoted as A.

[0089] S2. Mix A with solvent and trioleic acid glyceride in a mass ratio of 100:54:3 and ball mill at 300 r / min for 12 h to obtain B;

[0090] S3. Add polyvinyl butyral and dioctyl phthalate to B. The mass ratio of polyvinyl butyral and dioctyl phthalate to A is 2:2:25. After mixing, ball mill the mixture for the first time. The ball milling parameters are: ball milling time is 20h, ball milling speed is 300r / min, to obtain C.

[0091] S4. Debubbling C is then performed, followed by casting to obtain a film. The obtained film is then cut, stacked, and hot-pressed to obtain a ceramic preform. The ceramic preform is then isostatically pressed at 150 MPa for 2 minutes to obtain D.

[0092] S5. After holding the ceramic body at 550℃ for 2 hours to remove the glue, the body is then isostatically pressed at 200MPa for 1 minute to obtain a dense ceramic body, which is E.

[0093] S6. Place E into a muffle furnace for sintering. The sintering process is carried out in an oxygen atmosphere. The temperature is increased to 800℃ at a heating rate of 5℃ / min and held for 1 hour. Then the temperature is increased to 1200℃ at a heating rate of 8℃ / min and held for 1 hour. Then the temperature is decreased to 1150℃ at a heating rate of 8℃ / min and held for 20 hours. Finally, the temperature is decreased to 800℃ and held for 1 hour. The furnace is then cooled to room temperature to obtain a textured ceramic material with

[001] orientation, denoted as F.

[0094] S7. Polish both sides of F until smooth, then coat the silver electrode evenly, and finally polarize it in silicone oil. The polarization temperature is 150℃, the polarization voltage is 30kV / cm, and the polarization time is 15min. After polarization, the piezoelectric ceramic material is obtained.

[0095] Comparative Example 3

[0096] The comparative sample prepared with the following chemical formula is:

[0097] 0.07Pb(Sc 1 / 2 Nb 1 / 2 O3-0.35Pb(Mg)1 / 3 Nb 2 / 3 The specific preparation process of O3-0.2PbZrO3-0.38PbTiO3-0.01Eu2O3 is as follows:

[0098] S1. Prepare the ingredients according to the stoichiometric ratio, and ball mill using anhydrous ethanol as the ball milling medium. After ball milling, dry the powder and press it into... The block was pre-fired at 730℃ for 2 hours. After pre-firing, the block was ball-milled again for 20 hours to obtain perovskite phase powder, denoted as A.

[0099] S2. Mix A with solvent and trioleic acid glyceride in a mass ratio of 100:54:3 and ball mill at 300 r / min for 12 h to obtain B;

[0100] S3. Polyvinyl butyral and dioctyl phthalate were added to B, with a mass ratio of polyvinyl butyral and dioctyl phthalate to A of 2:2:25. After mixing, the mixture was ball-milled for the first time with the following parameters: ball-milling time of 20 h and ball-milling speed of 300 r / min. Then, a BaTiO3 template was added and ball-milled at low speed with the following parameters: ball-milling time of 0.5 h and ball-milling speed of 200 r / min, to obtain C.

[0101] S4. Debubbling C is then performed, followed by casting to obtain a film. The obtained film is then cut, stacked, and hot-pressed to obtain a ceramic preform. The ceramic preform is then isostatically pressed at 150 MPa for 2 minutes to obtain D.

[0102] S5. After holding the ceramic body at 550℃ for 2 hours to remove the glue, the body is then isostatically pressed at 200MPa for 1 minute to obtain a dense ceramic body, which is E.

[0103] S6. Sinter E at 1150℃ for 20h and allow it to cool naturally to obtain a

[001] oriented textured ceramic material, denoted as F;

[0104] S7. Polish both sides of F until smooth, then uniformly coat with silver electrodes, and finally polarize in silicone oil at a polarization temperature of 150℃, a polarization voltage of 30kV / cm, and a polarization time of 15min. After polarization, a piezoelectric ceramic material is obtained. The properties of the product prepared in this comparative example were measured, and it was found that the texture of the obtained textured ceramic was low, only 92.1%, and the piezoelectric constant was 850pC / N. PFM testing showed that the domain size was significantly smaller than that of Example 2.

[0105] The materials prepared in Comparative Examples 1 and 2, as well as in Example 2, were subjected to performance tests. Specific results are shown in [link to details]. Figure 1-4 As shown in the figure, we can see that: from Figure 1As can be seen from Example 2, the product prepared has a pure perovskite phase structure and high texture (F). 001 >98%); from Figure 3 It can be seen from the small amount of Eu doping 3+ Under these circumstances, the T of the textured ceramic product prepared in Example 2 c Basically unchanged; from Figure 4 The texture of Eu can be seen in 3+ The piezoelectric constant of PSN-PMN-PZ-PT textured ceramics is significantly improved compared to both randomly oriented and undoped textured ceramics, reaching a maximum of 1275 pC / N; from Figure 5 It can be seen that the textured ceramics obtained by the multi-stage sintering process have larger electric domain sizes.

[0106] Finally, it should be noted that the above descriptions are merely preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the claims of the present invention.

Claims

1. A high-performance PSN-PMN-PZ-PT quaternary textured piezoelectric ceramic material, characterized in that, The chemical formula is xPb(Sc) 1 / 2 Nb 1 / 2 O3-(1-xyz)Pb(Mg) 1 / 3 Nb 2 / 3 )O3-yPbZrO3-zPbTiO3-aEu2O3-bwt%BaTiO3, where x, y, z, and a all represent mole fractions, 0 <x≤0.15,0.1≤y≤0.25,0.32≤z≤0.4,0.005≤a≤0.02,1≤b≤5。 2. The high-performance PSN-PMN-PZ-PT quaternary textured piezoelectric ceramic material according to claim 1, characterized in that, The ceramic material has a perovskite structure.

3. The preparation method of a high-performance PSN-PMN-PZ-PT quaternary textured piezoelectric ceramic material as described in claim 1, characterized in that, Follow these steps in sequence: S1. The ingredients are prepared according to the stoichiometric ratio, and anhydrous ethanol is used as the ball milling medium for ball milling. After ball milling, the powder is dried and pressed into φ13mm blocks for pre-calcination. The pre-calcined blocks are ball milled again for 12-24h to obtain perovskite phase powder, denoted as A. S2. Mix A with solvent and trioleic acid glyceride, and ball mill for 12-24 hours to obtain B; S3. Add polyvinyl butyral and dioctyl phthalate to B, mix and ball mill for 12-24 hours, then add BaTiO3 template and ball mill at low speed for 0.5-1.5 hours to obtain C; S4. Degas C, then cast it to obtain a film. Cut, stack, and hot press the obtained film to obtain a ceramic preform. Then, isostatically press the ceramic preform at 150-230MPa for 2 minutes to obtain D. S5. After holding the body at 550-650℃ for 2 hours to remove the glue, the body is then isostatically pressed at 150-230MPa for 1 minute to obtain a dense ceramic body, E. S6. Place E into a muffle furnace for sintering. The sintering process is carried out in an oxygen atmosphere. The temperature is increased to 800℃ at a heating rate of 5℃ / min and held for 1 hour. Then the temperature is increased to 1200℃ at a heating rate of 8℃ / min and held for 1 hour. Then the temperature is decreased to 1150℃ at a heating rate of 8℃ / min and held for 20 hours. Finally, the temperature is decreased to 800℃ and held for 1 hour. The furnace is then cooled to room temperature to obtain a textured ceramic material with [001] orientation, denoted as F. S7. Polish the two sides of F perpendicular to the [001] orientation until smooth, then uniformly coat with silver electrodes, and finally polarize in silicone oil. After polarization, a piezoelectric ceramic material is obtained.

4. The method for preparing a high-performance PSN-PMN-PZ-PT quaternary textured piezoelectric ceramic material according to claim 3, characterized in that, In step S1, the pre-firing temperature is 750-820℃ and the pre-firing time is 2 hours.

5. The method for preparing a high-performance PSN-PMN-PZ-PT quaternary textured piezoelectric ceramic material according to claim 3, characterized in that, In step S2, the solvent is a mixture of anhydrous ethanol and butanone in a mass ratio of 1:2, and the mass ratio of the solvent, trioleic acid glyceride and A is 54:3:

100.

6. The method for preparing a high-performance PSN-PMN-PZ-PT quaternary textured piezoelectric ceramic material according to claim 3, characterized in that, In step S3, the mass ratio of polyvinyl butyral, dioctyl phthalate, and A is 2:2:

25.

7. The method for preparing a high-performance PSN-PMN-PZ-PT quaternary textured piezoelectric ceramic material according to claim 3, characterized in that, In step S3, the ball milling speed for the first ball mill is 280-350 r / min, and the low-speed ball milling speed is 150-250 r / min.

8. The method for preparing a high-performance PSN-PMN-PZ-PT quaternary textured piezoelectric ceramic material according to claim 3, characterized in that, In step S2, the ball mill rotation speed is 280-350 r / min.

9. A method for preparing a high-performance PSN-PMN-PZ-PT quaternary textured piezoelectric ceramic material according to any one of claims 3-8, characterized in that, In step S7, the polarization temperature is 150℃, the polarization voltage is 30kV / cm, and the polarization time is 15min.

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