High-entropy biological piezoelectric ceramic and preparation method thereof

Abstract

The invention belongs to the technical field of high-entropy ceramic materials, and particularly relates to high-entropy biological piezoelectric ceramic and a preparation method thereof. The structure of the high-entropy biological piezoelectric ceramic disclosed by the invention is an ABO3 type perovskite structure; according to the invention, Bi < 0.5 > Na < 0.5 > TiO < 3 > is used as a matrix, Zr and Sn or Zr, Sn and Hf are doped at a B site according to an equal molar ratio, and the high-entropy biological piezoelectric ceramic with a chemical formula of (Bi < 0.5 > Na < 0.5 >) (Zr < 1 / 3 > Ti < 1 / 3 > Sn < 1 / 3 >) O < 3 > or (Bi < 0.5 > Na < 0.5 >) (Zr < 0.25 > Ti < 0.25 > Sn < 0.25 > Hf < 0.25 >) O < 3 > is obtained. The high-entropy biological piezoelectric ceramic prepared by the method disclosed by the invention has good piezoelectric property.

Description

Technical Field

[0001] The invention belongs to the technical field of high entropy ceramic materials, and in particular relates to a high entropy bio-piezoelectric ceramic and a preparation method thereof. Background Art

[0002] Biopiezoelectric ceramics have good osteogenic activity due to their piezoelectric effect similar to natural bone tissue, and have attracted great attention from bone tissue engineering researchers. They are a new type of bioactive material that is different from conductive materials. This material can be linked to the proliferation and differentiation behavior of osteoblasts in organisms through electrical signals and promote bone repair, and has good development prospects.

[0003] The piezoelectric performance of traditional single-component piezoelectric ceramic systems is relatively low, and single-component piezoelectric ceramics cannot meet the needs of social development for high-performance new materials. Existing technologies develop multi-component composite piezoelectric ceramic systems in order to obtain high-performance bio-piezoelectric ceramics. However, multi-component piezoelectric ceramics still have the problem of low solid solubility, which affects the piezoelectric performance of the material. Summary of the invention

[0004] In order to solve the above technical problems, the present invention provides a high-entropy bio-piezoelectric ceramic and a preparation method thereof.

[0005] The first object of the present invention is to provide a high entropy bio-piezoelectric ceramic, the structure of the high entropy bio-piezoelectric ceramic of the present invention is an ABO3 type perovskite structure; 0.5 Na 0.5 TiO3 is used as the matrix, and Zr and Sn or Zr, Sn and Hf are doped at the B position in an equal molar ratio to obtain a chemical formula of (Bi 0.5 Na 0.5 )(Zr 1 / 3 Ti 1 / 3 Sn 1 / 3 )O3 or (Bi 0.5 Na 0.5 )(Zr 0.25 Ti 0.5 Sn 0.25 Hf 0.25 )O3 high entropy bio-piezoelectric ceramics.

[0006] In the early exploration process, the present invention used the traditional idea of ​​constructing piezoelectric ceramics, that is, to adjust the composition and structure to prepare piezoelectric ceramics through component design; therefore, a large number of component experiments were designed, which made the amount of experiments and analysis huge. And if all components need to be tested, the current experimental methods and time conditions are almost difficult to achieve. The present invention uses the "quasi-isotropic phase boundary construction" method to reduce the experimental workload and improve the piezoelectric performance to prepare piezoelectric ceramics; however, when the number of components in the system is more, the same problem is faced, so new design ideas are needed when designing multi-component piezoelectric ceramics.

[0007] The present invention adopts the design concept and preparation strategy of high entropy alloy to prepare biological piezoelectric ceramics, and increases the ability to form a single-phase solid solution by increasing the solid solubility limit between components to obtain a new multi-principal component single-phase solid solution ceramic material. The present invention selects the BNT system with excellent piezoelectric and ferroelectric properties to directly dope and modify to obtain high entropy piezoelectric ceramics. 0.5 Na 0.5 TiO3, abbreviated as BNT, is a perovskite-type relaxor ferroelectric.

[0008] The present invention uses BNT as a matrix, and uses Bi2O3, Na2CO3, TiO2, ZrO2, SnO2 and HfO2 powders as raw materials. Zr and Sn or Zr, Sn and Hf are doped at the B position in an equal molar ratio, and after solid phase sintering, (Bi 0.5 Na 0.5 )(Zr 1 / 3Ti 1 / 3 Sn 1 / 3 )O3 or (Bi 0.5 Na 0.5 )(Zr 0.25 Ti 0.25 Sn 0.25 Hf 0.25 )O3 high entropy bio-piezoelectric ceramics.

[0009] The second object of the present invention is to provide a method for preparing a high entropy biopiezoelectric ceramic, comprising the following steps: Step 1: Using Bi2O3, Na2CO3, TiO2, ZrO2, SnO2 and HfO2 powder as raw materials, according to the general formula (Bi 0.5 Na 0.5 )(Zr 1 / 3 Ti 1 / 3 Sn 1 / 3 )O3 or (Bi 0.5 Na 0.5 )(Zr 0.25 Ti 0.25 Sn 0.25 Hf 0.25 )O3 stoichiometric ratio was used to weigh the raw materials.

[0010] It should be noted that, according to the theory of "tolerance factor" of doping, the present invention preferably "dopes" Zr, Sn and Hf elements with the same valence as "Ti" in BNT, and the chemical properties and ionic radius of the four elements Ti, Zr, Sn and Hf are similar. According to the principle of crystal chemistry and ionic radius matching, the three elements Zr, Ti and Sn or the four elements Zr, Ti, Sn and Hf can be doped into the B position of the BNT lattice in an equal molar ratio. After doping, the four elements Zr, Ti, Sn and Hf occupy the B position lattice in an equal molar ratio, which causes lattice distortion relative to the original BNT matrix crystal structure. The high entropy effect corresponding to the multi-principal ceramic promotes the formation of solid solution, which is beneficial to improve the piezoelectric effect of BNT ceramics; at the same time, the BNT lattice is activated by forming a solid solution, ion vacancies are generated, diffusion is promoted, and the sintering temperature is reduced.

[0011] Step 2: wet ball milling the raw materials, and then drying and pre-calcining to obtain reaction powder.

[0012] The present invention wet-mills the raw materials to obtain a uniform raw material mixture and improves the reactivity of the powder. The wet-milling medium is anhydrous ethanol. The raw materials after ball milling are dried and pre-burned, which is conducive to the initial reaction of the raw materials, generates precursors, and improves the effect of subsequent sintering.

[0013] Preferably, the drying temperature is 30° C. to 80° C., and the drying time is 10 h to 12 h.

[0014] Preferably, the pre-firing temperature is 600° C. to 900° C., and the pre-firing time is 3 h to 5 h.

[0015] Step 3: ball-mill the reaction powder for a second time, dry it, add paraffin wax to granulate it, and press it into a shape to obtain a ceramic green body.

[0016] Preferably, the conditions for the primary ball milling and the secondary ball milling are: the ball milling time is 2h~24h, the rotation speed of the ball mill is 4000rpm~5000rpm, and the ball milling medium is anhydrous ethanol.

[0017] Preferably, the diameter of the mold used for the compression molding is 11 mm to 12 mm, the pressure is 4 MPa to 5 MPa, and the holding time is 4 s to 5 s.

[0018] Preferably, the amount of the paraffin wax is 7% to 8% of the total mass of the reaction powder.

[0019] Step 4: Place the ceramic green body into a tubular furnace and calcine it at 1000° C. to 1200° C. to obtain high-entropy bio-piezoelectric ceramics.

[0020] The ceramic green body is calcined at high temperature in a tube furnace to promote the solid phase reaction of the reaction powder and form a stable ceramic phase structure. High temperature calcination can improve the density and mechanical properties of the ceramic material. Preferably, during the calcination process, the temperature is raised from room temperature to 1000°C to 1200°C at a heating rate of 3°C / min to 4°C / min, and the holding time in the tube furnace is 2h to 6h, and then cooled to room temperature with the furnace.

[0021] Compared with the prior art, the present invention has the following beneficial effects: The present invention uses Zr, Sn and Hf elements with the same valence as "Ti" in BNT for "same-valence doping", and the chemical properties and ionic radius of the four elements Ti, Zr, Sn and Hf are similar. The three elements Zr, Ti and Sn or the four elements Zr, Ti, Sn and Hf can be doped into the B site of the BNT lattice in an equimolar ratio. Compared with the original BNT matrix crystal structure, the equimolar doping of the B site induces lattice distortion, and the high entropy effect corresponding to the multi-principal component ceramics promotes the formation of solid solution, which is beneficial to improving the piezoelectric effect of BNT ceramics; at the same time, the BNT lattice is activated by forming a solid solution, ion vacancies are generated, diffusion is promoted, and the sintering temperature is reduced. The (Bi 0.5 Na 0.5 )(Zr 1 / 3 Ti 1 / 3 Sn 1 / 3 )O3 high entropy bio-piezoelectric ceramics have a piezoelectric constant of 75pC / N, (Bi 0.5 Na 0.5 )(Zr 0.25 Ti 0.25 Sn 0.25 Hf 0.25 ) The piezoelectric constant of the O3 high entropy bio-piezoelectric ceramic is 80pC / N. The high entropy bio-piezoelectric ceramic prepared by the present invention has good piezoelectric properties.

[0022] The preparation process of the invention is simple, does not require atmosphere sintering, and has the characteristics of short sintering time, low sintering temperature, simple process and high efficiency. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 The (Bi 0.5 Na 0.5 )(Zr 0.5 Ti 0.5 )O3, (Bi prepared in Example 1 0.5 Na 0.5 )(Zr 1 / 3 Ti 1 / 3 Sn 1 / 3 )O3 and (Bi prepared in Example 2 0.5 Na 0.5)(Zr 0.25 Ti 0.25 Sn 0.25 Hf 0.25 )Piezoelectric constant of O3 biopiezoelectric ceramics. DETAILED DESCRIPTION

[0024] In order to enable those skilled in the art to better understand and implement the technical solution of the present invention, the present invention is further described below in conjunction with specific embodiments and drawings.

[0025] In the description of the present invention, unless otherwise specified, all reagents used are commercially available and all methods used are conventional techniques in the art.

[0026] Example 1 This embodiment provides a high-entropy bio-piezoelectric ceramic.

[0027] In this embodiment, Bi 0.5 Na 0.5 TiO3 is used as the matrix, and Zr and Sn are doped at the B position in an equal molar ratio to obtain a chemical formula of (Bi 0.5 Na 0.5 )(Zr 1 / 3 Ti 1 / 3 Sn 1 / 3 )O3 high entropy bio-piezoelectric ceramics.

[0028] The high entropy bio-piezoelectric ceramic of this embodiment is prepared by the following steps: Step 1: Using Bi2O3, Na2CO3, TiO2, ZrO2 and SnO2 powder as raw materials, 0.5 Na 0.5 )(Zr 0.25 Ti 1 / 3Sn 1 / 3 )Weigh the raw materials in the stoichiometric ratio in the O3 chemical formula.

[0029] Step 2: Prepare reaction powder: 2.1) Place all raw materials in a nylon jar, add 40 mL of ethanol and shake evenly, then perform ball milling for 12 h at a ball mill speed of 4000 rpm to obtain a slurry.

[0030] 2.2) The slurry was placed in an oven and dried at 70°C for 12 h, and then placed in a tubular furnace and pre-calcined at 850°C for 4.7 h to obtain a reaction powder.

[0031] Step 3: preparing ceramic green body: 3.1) Place the reaction powder in a nylon jar, add 40 mL of ethanol and shake evenly, then perform secondary ball milling for 12 h at a ball mill speed of 4000 rpm.

[0032] 3.2) The mixed reaction powder is dried at 70°C for 12 hours, and then paraffin is added for granulation to obtain a precursor powder; wherein the mass of the paraffin is 8% of the mass of the reaction powder.

[0033] 3.3) The precursor powder was pressed into a ceramic green body with a diameter of 11 mm under a uniaxial pressure of 5 MPa and the holding time was 4 s.

[0034] Step 4: Place the ceramic green body in a tubular furnace and heat the temperature from room temperature to 1050°C at a heating rate of 3°C / min for calcination. The heat preservation time is 4 hours, and then the green body is cooled to room temperature to obtain a high entropy bio-piezoelectric ceramic, namely (Bi 0.5 Na 0.5 )(Zr 1 / 3 Ti 1 / 3 Sn 1 / 3 )O3.

[0035] Example 2 This embodiment provides a high-entropy bio-piezoelectric ceramic.

[0036] In this embodiment, Bi 0.5 Na 0.5 TiO3 is used as the matrix, and Zr, Sn and Hf are doped at the B position in an equal molar ratio to obtain a chemical formula of (Bi 0.5 Na 0.5 )(Zr 0.25 Ti 0.25 Sn 0.25 Hf 0.25 )O3 high entropy bio-piezoelectric ceramics.

[0037] The high entropy bio-piezoelectric ceramic of this embodiment is prepared by the following steps: Step 1: Using Bi2O3, Na2CO3, TiO2, ZrO2, SnO2 and HfO2 powder as raw materials, 0.5 Na 0.5 )(Zr 0.25 Ti 0.25 Sn 0.25 Hf 0.25 )Weigh the raw materials in the stoichiometric ratio in the O3 chemical formula.

[0038] Step 2: Prepare reaction powder: 2.1) Place all raw materials in a nylon jar, add 40 mL of ethanol and shake evenly, then perform ball milling for 12 h at a ball mill speed of 4000 rpm to obtain a slurry.

[0039] 2.2) The slurry was placed in an oven and dried at 80°C for 12 hours, and then placed in a tubular furnace and pre-calcined at 850°C for 4.5 hours to obtain a reaction powder.

[0040] Step 3: preparing ceramic green body: 3.1) Place the reaction powder in a nylon jar, add 40 mL of ethanol and shake evenly, then perform secondary ball milling for 12 h at a ball mill speed of 4000 rpm.

[0041] 3.2) The mixed reaction powder is dried at 80°C for 12 hours, and paraffin is added for granulation to obtain a precursor powder; wherein the mass of the paraffin is 9% of the mass of the reaction powder.

[0042] 3.3) The precursor powder was pressed into a ceramic green body with a diameter of 12 mm under a uniaxial pressure of 4 MPa and the holding time was 5 s.

[0043] Step 4: Place the ceramic green body in a tubular furnace and heat the temperature from room temperature to 1050°C at a heating rate of 4°C / min for calcination. The heat preservation time is 4 hours, and then the green body is cooled to room temperature to obtain a high entropy bio-piezoelectric ceramic, namely (Bi 0.5 Na 0.5 )(Zr 0.25 Ti 0.25 Sn 0.25 Hf 0.25 )O3.

[0044] Example 3 This embodiment provides a high-entropy bio-piezoelectric ceramic.

[0045] In this embodiment, Bi 0.5 Na 0.5 TiO3 is used as the matrix, and Zr, Sn and Hf are doped at the B position in an equal molar ratio to obtain a chemical formula of (Bi 0.5 Na 0.5 )(Zr 0.25 Ti 0.25 Sn 0.25 Hf 0.25 )O3 high entropy bio-piezoelectric ceramics.

[0046] The high entropy bio-piezoelectric ceramic of this embodiment is prepared by the following steps: Step 1: Using Bi2O3, Na2CO3, TiO2, ZrO2, SnO2 and HfO2 powder as raw materials, 0.5 Na 0.5 )(Zr 0.25 Ti 0.25 Sn 0.25 Hf 0.25 )Weigh the raw materials in the stoichiometric ratio in the O3 chemical formula.

[0047] Step 2: Prepare reaction powder: 2.1) Place the above raw materials in a nylon jar, add 40 mL of ethanol and shake evenly, then perform ball milling for 2 h at a ball mill speed of 4000 rpm to obtain a slurry.

[0048] 2.2) The slurry was placed in an oven and dried at 30°C for 10 h, and then placed in a tubular furnace and pre-calcined at 600°C for 3 h to obtain a reaction powder.

[0049] Step 3: preparing ceramic green body: 3.1) Place the reaction powder in a nylon jar, add 40 mL of ethanol and shake it evenly. Perform secondary ball milling for 10 h at a ball mill speed of 4000 rpm.

[0050] 3.2) The mixed reaction powder is dried at 30°C for 10 hours, and paraffin is added for granulation to obtain a precursor powder; wherein the mass of the paraffin is 9% of the mass of the reaction powder.

[0051] 3.3) The precursor powder was pressed into a ceramic green body with a diameter of 11 mm under a uniaxial pressure of 4 MPa and the holding time was 4 s.

[0052] Step 4: Place the ceramic green body in a tubular furnace and heat it from room temperature to 1000°C at a heating rate of 4°C / min for calcination. The heat preservation time is 2 hours, and then the green body is cooled to room temperature in the furnace to obtain a high-entropy bio-piezoelectric ceramic.

[0053] Example 4 This embodiment provides a high-entropy bio-piezoelectric ceramic.

[0054] In this embodiment, Bi 0.5 Na 0.5 TiO3 is used as the matrix, and Zr, Sn and Hf are doped at the B position in an equal molar ratio to obtain a chemical formula of (Bi 0.5 Na 0.5 )(Zr 0.25 Ti 0.25 Sn 0.25 Hf 0.25 )O3 high entropy bio-piezoelectric ceramics.

[0055] The high entropy bio-piezoelectric ceramic of this embodiment is prepared by the following steps: Step 1: Using Bi2O3, Na2CO3, TiO2, ZrO2, SnO2 and HfO2 powder as raw materials, 0.5 Na 0.5 )(Zr 0.25 Ti 0.25 Sn 0.25 Hf 0.25 )Weigh the raw materials in the stoichiometric ratio in the O3 chemical formula.

[0056] Step 2: Prepare reaction powder: 2.1) Place all raw materials in a nylon jar, add 40 mL of ethanol and shake evenly, then perform ball milling for 2 h at a ball mill speed of 4000 rpm to obtain a slurry.

[0057] 2.2) The slurry was placed in an oven and dried at 80°C for 12 hours, and then placed in a tubular furnace and pre-calcined at 900°C for 5 hours to obtain a reaction powder.

[0058] Step 3: preparing ceramic green body: 3.1) Place the reaction powder in a nylon jar, add 40 mL of ethanol and shake evenly, then perform secondary ball milling for 24 h at a ball mill speed of 5000 rpm.

[0059] 3.2) The mixed reaction powder is dried at 80°C for 12 hours, and then paraffin is added for granulation to obtain a precursor powder; wherein the mass of the paraffin is 9% of the mass of the reaction powder.

[0060] 3.3) The precursor powder was pressed into a ceramic green body with a diameter of 12 mm under a uniaxial pressure of 5 MPa and the holding time was 5 s.

[0061] Step 4: Place the ceramic green body in a tubular furnace and heat it from room temperature to 1200°C at a heating rate of 4°C / min for calcination. The heat preservation time is 6 hours, and then cool it to room temperature with the furnace to obtain high entropy bio-piezoelectric ceramics.

[0062] Comparative Example 1 This comparative example provides a medium-entropy bio-piezoelectric ceramic.

[0063] This comparative example is based on Bi 0.5 Na 0.5 TiO3 is used as the matrix and Zr is doped at the B position in an equal molar ratio to obtain the chemical formula (Bi 0.5 Na 0.5 )(Zr 0.5 Ti 0.5 )O3 medium-entropy bio-piezoelectric ceramics.

[0064] The medium entropy bio-piezoelectric ceramic of this comparative example is prepared by the following steps: Step 1: Using Bi2O3, Na2CO3, TiO2 and ZrO2 powder as raw materials, 0.5 Na 0.5 )(Zr 0.5 Ti 0.5 )Weigh the raw materials in the stoichiometric ratio in the O3 chemical formula.

[0065] Step 2: Prepare reaction powder: 2.1) Place all raw materials in a nylon jar, add 40 mL of ethanol and shake evenly, then perform ball milling for 12 h at a ball mill speed of 4000 rpm to obtain a slurry.

[0066] 2.2) The slurry was placed in an oven and dried at 70°C for 12 hours, and then placed in a tubular furnace and pre-calcined at 850°C for 4.7 hours to obtain a reaction powder.

[0067] Step 3: preparing ceramic green body: 3.1) Place the reaction powder in a nylon jar, add 40 mL of ethanol and shake evenly, then perform secondary ball milling for 12 h at a ball mill speed of 4000 rpm.

[0068] 3.2) The mixed reaction powder is dried at 70°C for 10 hours, and then paraffin is added for granulation to obtain a precursor powder; wherein the mass of the paraffin is 9% of the mass of the reaction powder.

[0069] 3.3) The precursor powder was pressed into a ceramic green body with a diameter of 11 mm under a uniaxial pressure of 4 MPa.

[0070] Step 4: Place the ceramic green body in a tubular furnace and heat the temperature from room temperature to 1050°C at a heating rate of 3°C / min for calcination. The heat preservation time is 4 hours, and then the green body is cooled to room temperature in the furnace to obtain a medium entropy bio-piezoelectric ceramic, namely (Bi 0.5 Na 0.5 )(Zr 0.5 Ti 0.5 )O3.

[0071] Experimental test: 1. Mixed entropy The present invention calculates the mixing entropy values ​​of the bio-piezoelectric ceramics prepared in Example 1, Example 2 and Comparative Example 1 according to the mixing entropy value formula, and the mixing entropy values ​​are shown in Table 1.

[0072] Mixing entropy S config =-R[ ], where x a 、x b and x c They refer to the molar fractions of A-site, B-site and C-site ions respectively. A-site refers to the A site, B-site refers to the B site, and C-site refers to the C site.

[0073] Table 1 Mixing entropy values ​​of biopiezoelectric ceramics prepared in Example 1, Example 2 and Comparative Example 1 It can be seen from Table 1 that with the increase of doping elements, the doping elements are doped into the B site of the BNT lattice in an equal molar ratio, and the multi-principal element ceramics formed increase the high entropy effect.

[0074] 2. Piezoelectric test According to the GB / T3389 2008 test standard, the ceramic samples prepared in Examples 1 to 2 and Comparative Example 1 were polished, cleaned and dried respectively, and the upper and lower ends of the ceramic samples were silvered and dried to obtain polarized ceramic samples; the upper and lower surfaces of the polarized ceramic samples were placed between the two electrodes of the test bench, and the distance between the two electrodes was adjusted until the ceramic sample and the fixture of the stage did not vibrate, and data was read. The piezoelectric constant test was carried out using the SA1303A quasi-static d 33 Measuring instrument, the test temperature is room temperature. Piezoelectric constant d 33 The results are as follows Figure 1 shown.

[0075] Figure 1 (Bi prepared in Comparative Example 1 0.5 Na 0.5 )(Zr 0.5 Ti 0.5 )O3, (Bi prepared in Example 1 0.5 Na 0.5 )(Zr 1 / 3Ti 1 / 3 Sn 1 / 3 )O3 and (Bi prepared in Example 2 0.5 Na 0.5 )(Zr 0.25 Ti 0.25 Sn 0.25 Hf 0.25 )Piezoelectric constant of O3 biopiezoelectric ceramics. Figure 1 It can be seen that the piezoelectric constants of the high entropy biopiezoelectric ceramics prepared in Comparative Example 1, Example 1 and Example 2 are 60pC / N, 80pC / N and 75pC / N, respectively. Compared with Comparative Example 1, the piezoelectric properties of the high entropy biopiezoelectric ceramics prepared in Example 1 and Example 2 are improved. This is because the molar ratio of the doped elements occupies the B-site lattice, causing lattice distortion. At the same time, the high entropy effect corresponding to the multi-principal ceramics promotes the formation of solid solution; the high entropy effect and the lattice distortion effect synergistically promote the improvement of the piezoelectric properties of BNT ceramics; and the piezoelectric constant of the high entropy biopiezoelectric ceramics prepared in Example 2 is slightly lower than that of the high entropy biopiezoelectric ceramics prepared in Example 1, which may be due to the slightly excessive element doping that destroys the ceramic solid solubility and the final crystal structure to a certain extent.

[0076] XRD test shows that the (Bi 0.5 Na0.5 )(Zr 0.25 Ti 0.25 Sn 0.25 Hf 0.25 )O3 high-entropy bio-piezoelectric ceramics have similar characteristic peaks, indicating that they have the same phase structure and similar piezoelectric properties.

[0077] It should be noted that when the present invention involves a numerical range, it should be understood that the two endpoints of each numerical range and any value between the two endpoints can be selected. Since the steps and methods used are the same as those in the embodiments, in order to avoid redundancy, the present invention describes a preferred embodiment. Although the preferred embodiments of the present invention have been described, once those skilled in the art know the basic creative concept, they can make other changes and modifications to these embodiments, and these changes and modifications all fall within the scope of the present invention.

[0078] Obviously, those skilled in the art can make various changes and modifications to the present invention without departing from the spirit and scope of the present invention. If these modifications and variations of the present invention fall within the scope of the equivalent technology of the present invention, the present invention is also intended to include these modifications and variations.

Claims

1. A high entropy bio-piezoelectric ceramic, characterized in that: The structure of the high entropy bio-piezoelectric ceramic is an ABO3 type perovskite structure; Bi 0.5 Na 0.5 TiO3 is used as the matrix, and Zr and Sn or Zr, Sn and Hf are doped at the B position in an equal molar ratio to obtain a chemical formula of (Bi 0.5 Na 0.5 )(Zr 1 / 3 Ti 1 / 3 Sn 1 / 3 )O3 or (Bi 0.5 Na 0.5 )(Zr 0.25 Ti 0.25 Sn 0.25 Hf 0.25 )O3 high entropy bio-piezoelectric ceramics.

2. The method for preparing the high entropy biopiezoelectric ceramic according to claim 1, characterized in that: The following steps are involved: Using Bi2O3, Na2CO3, TiO2, ZrO2, SnO2 and HfO2 powder as raw materials, according to the general formula (Bi 0.5 Na 0.5 )(Zr 1 / 3 Ti 1 / 3Sn 1 / 3 )O3 or (Bi 0.5 Na 0.5 )(Zr 0.25 Ti 0.25 Sn 0.25 Hf 0.25 ) Weigh each raw material in a stoichiometric ratio of O3; The raw materials are wet ball-milled and mixed, and then dried and pre-calcined to obtain reaction powder; The reaction powder is ball-milled for a second time, dried, and granulated and pressed into shape by adding paraffin wax to obtain a ceramic green body; The ceramic green body is placed in a tubular furnace and calcined at 1000°C to 1200°C to obtain high-entropy bio-piezoelectric ceramics.

3. The method for preparing the high entropy bio-piezoelectric ceramic according to claim 1, characterized in that: During the calcination process, the temperature is raised from room temperature to 1000°C to 1200°C at a heating rate of 3°C / min to 4°C / min, kept at that temperature for 2h to 6h, and then cooled to room temperature along with the furnace.

4. The method for preparing the high entropy bio-piezoelectric ceramic according to claim 1, characterized in that: The pre-firing temperature is 600° C. to 900° C., and the pre-firing time is 3 h to 5 h.

5. The method for preparing the high entropy biopiezoelectric ceramic according to claim 1, characterized in that: The pressing pressure is 4MPa~5MPa, and the holding time is 3s~4s.

6. The method for preparing high entropy biopiezoelectric ceramics according to claim 1, characterized in that: The conditions of the primary ball milling and the secondary ball milling are as follows: the ball milling time is 2h-24h, the rotation speed of the ball mill is 4000rpm-5000rpm, and the ball milling medium is anhydrous ethanol.

7. The method for preparing high entropy biopiezoelectric ceramics according to claim 1, characterized in that: The mass of the paraffin wax is 7% to 8% of the total mass of the reaction powder.

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