High-transparency lead-free perovskite ceramic material and preparation method thereof

Abstract

The application discloses a high-transparency lead-free perovskite ceramic material and a preparation method thereof, relates to the technical field of piezoelectric ceramic dielectric materials, and comprises the following steps: mixing BaCO3, CaCO3, ZrO2, TiO2 and Bi2O3, CuO and WO3 to obtain a mixture; sequentially performing ball milling, drying and pre-sintering on the mixture to obtain a main crystal phase powder; and sequentially performing ball milling and drying on the main crystal phase powder, and then performing granulation, tabletting and sintering in sequence to obtain the lead-free perovskite ceramic material. 3 / 4W 1 / 4 )O3 is dissolved into (Ba 0.85 Ca 0.15 )(Zr 0.1 Ti 0.9 )O3 to prepare the lead-free perovskite ceramic material, large crystal lattice distortion is generated in the lead-free perovskite ceramic material, good piezoelectric performance can be obtained, and the lead-free perovskite ceramic material has relatively good transmittance after polarization.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of piezoelectric ceramic dielectric materials, in particular to a high-transparency lead-free perovskite ceramic material and a preparation method thereof. BACKGROUND

[0002] Lead-free perovskite ceramic materials have become a key research direction in the field of piezoelectric ceramic dielectric materials due to their green nature. At present, BCZT ceramic materials ((Ba 0.85 Ca 0.15 )(Zr 0.1 Ti 0.9 )O3) have a high piezoelectric property due to a large number of internal domains, have a good application prospect in the piezoelectric direction, and have attracted much attention from many scientific researchers in recent years. However, pure BCZT-based ceramic has low Curie temperature, high polarization difficulty, and low transparency, and thus it is necessary to study doped lead-free perovskite ceramic materials.

[0003] In the prior art, Chinese patent CN114804865A discloses a preparation method of barium calcium zirconate titanate transparent ceramic, including the following steps: (1) batching: the chemical composition general formula is xBa(Zr 0.2 Ti 0.8 )O3-(1-x) 0.5 (Ba 0.7 Ca 0.3 )TiO3, raw materials BaTiO3, ZrO2, CaCO3, TiO2 are weighed according to the stoichiometric ratio, ball milling medium is first added into a ball mill tank, then the weighed raw materials are sequentially added into the ball mill tank, and then a liquid is added; (2) ball milling; (3) sand milling; (4) drying; (5) grinding and sieving: (6) calcining; (7) sintering: the calcined powder is placed in an SPS sintering furnace for sintering; (8) annealing; and barium calcium zirconate titanate transparent ceramic is obtained.

[0004] The ceramic material prepared by the above prior art has a transmittance of 10.1% at a thickness of 0.6 mm, the transmittance is low, and the piezoelectric property needs to be improved. SUMMARY

[0005] The present application provides a high-transparency lead-free perovskite ceramic material and a preparation method thereof, to solve the problems of low transmittance and piezoelectric property to be improved of the existing piezoelectric ceramic dielectric material.

[0006] In one aspect, the present application provides a preparation method of a high-transparency lead-free perovskite ceramic material, including the following steps:

[0007] Step one, BaCO3, CaCO3, ZrO2, TiO2 and Bi2O3, CuO, WO3 are mixed to obtain a mixture.

[0008] Step two, the mixture is sequentially subjected to ball milling, drying and pre-sintering to obtain the main crystal phase powder.

[0009] Step three, the main crystal phase powder is sequentially subjected to ball milling, drying, granulation, tabletting and sintering to obtain the lead-free perovskite ceramic material.

[0010] In a possible implementation, in step one, the molar ratio of BaCO3, CaCO3, ZrO2, TiO2 and Bi2O3, CuO, WO3 is calculated according to the molar ratio of (Ba 0.85 Ca 0.15 )(Zr 0.1 Ti 0.9 )O3 and Bi(Cu 3 / 4W 1 / 4 )O3, wherein x is 0.001-0.02.

[0011] In a possible implementation, in step two, the ball milling time is 12h, and anhydrous ethanol and zirconia ball stones are added during ball milling, and the mass ratio of the mixture, anhydrous ethanol and zirconia ball stones is 1:1.5:2.

[0012] In step two, the drying time is 2-4h, and the drying temperature is 80-100℃.

[0013] In a possible implementation, in step two, the pre-sintering temperature is 1000℃-1200℃, the holding time is 3-5h, and the heating rate is 3-5℃ / min.

[0014] In a possible implementation, in step three, the ball milling time is 8h, and anhydrous ethanol and zirconia ball stones are added during ball milling, and the mass ratio of the main crystal phase powder, anhydrous ethanol and zirconia ball stones is 1:1.5:2.

[0015] In step three, the drying time is 2-4h, and the drying temperature is 80-100℃.

[0016] In a possible implementation, in step three, a binder with a mass concentration of 5%-7% is added to the main crystal phase powder after drying for granulation, and particles between 60-80 meshes are screened out using a 60-mesh and an 80-mesh sieve for tabletting.

[0017] The binder is polyvinyl alcohol.

[0018] The tabletting pressure is 8-20MPa.

[0019] In a possible implementation, in step three, when sintering the ceramic green body obtained after tabletting, the temperature is first raised to 600 DEG C at a rate of 3 DEG C / min, and the temperature is kept constant for 2-4 h to remove glue, then the temperature is raised to 1400-1500 DEG C at the same rate, and the temperature is kept constant for 3-4 h, then the temperature is lowered to 700 DEG C at a rate of 5 DEG C / min, and the lead-free perovskite ceramic material is obtained after natural cooling.

[0020] In another aspect, the application provides a high-transparency lead-free perovskite ceramic material, which is formed by solid solution of (Ba 0.85 Ca 0.15 )(Zr 0.1 Ti 0.9 )O3 and Bi(Cu 3 / 4 W 1 / 4 )O3, i.e., is prepared by using the above preparation method of the high-transparency lead-free perovskite ceramic material.

[0021] The high-transparency lead-free perovskite ceramic material and the preparation method thereof in the application have the following advantages:

[0022] By designing the preparation method, Bi(Cu 3 / 4 W 1 / 4 )O3 is solid-soluted into (Ba 0.85 Ca 0.15 )(Zr 0.1 Ti 0.9 )O3, and the lead-free perovskite ceramic material prepared therefrom has large internal lattice distortion, can obtain good piezoelectric properties, and has relatively good transmittance after polarization. The piezoelectric property d 33 coefficient can reach 724 pC / N, and the transmittance T after polarization can reach 30%.

[0023] The lead-free perovskite ceramic material formed by solid solution of (Ba 0.85 Ca 0.15 )(Zr 0.1 Ti 0.9 )O3 and Bi(Cu 3 / 4 W 1 / 4 )O3 has simple preparation process, low cost, is suitable for mass production, and does not contain lead in raw materials, belongs to an environment-friendly ceramic material, and meets the needs of social development. BRIEF DESCRIPTION OF DRAWINGS

[0024] In order to more clearly illustrate the technical solutions in the embodiments of the application or the prior art, the following will briefly introduce the drawings needed to be used in the embodiments or the prior art description. Obviously, the drawings in the following description only some embodiments of the application, and for those skilled in the art, other drawings can also be obtained without creative labor.

[0025] Figure 1 A flowchart of a preparation method of a high-transparency lead-free perovskite ceramic material provided in an embodiment of the present application is shown in the figure;

[0026] Figure 2 The piezoelectric performance d of the lead-free perovskite ceramic material provided in Embodiments 1 to 6 of the present application is shown in the figure; 33 The coefficient fitting curve is shown in the figure.

[0027] Figure 3 The transmittance curves of the lead-free perovskite ceramic material provided in Embodiment 4 of the present application before and after polarization are shown in the figure;

[0028] Figure 4 The visible light photos of the lead-free perovskite ceramic material provided in Embodiment 4 of the present application before and after polarization are compared in the figure;

[0029] Figure 5 The strain field analysis schematic diagram of the high-angle annular dark field imaging of the lead-free perovskite ceramic material provided in Embodiment 4 of the present application is shown in the figure. DETAILED DESCRIPTION

[0030] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0031] As shown in the figure, Figure 1 the present application provides a preparation method of a high-transparency lead-free perovskite ceramic material, comprising the following steps:

[0032] Step one, BaCO3, CaCO3, ZrO2, TiO2 and Bi2O3, CuO, WO3 are mixed to obtain a mixture.

[0033] Step two, the mixture is sequentially subjected to ball milling, drying and pre-sintering to obtain a main crystal phase powder.

[0034] Step three, the main crystal phase powder is sequentially subjected to ball milling and drying, and then sequentially subjected to granulation, tabletting and sintering to obtain a lead-free perovskite ceramic material.

[0035] Specifically, the chemical reactions of BaCO3, CaCO3, ZrO2 and TiO2 at high temperature are as shown below:

[0036] 0.85BaCO3+0.15CaCO3+0.1ZrO2+0.9TiO2(high temperature)→(Ba 0.85 Ca0.15 )(Zr 0.1 Ti 0.9 )O3+CO2.

[0037] The chemical reactions of Bi2O3, CuO, WO3 at high temperature are shown as follows:

[0038] Bi2O3+1.5CuO+0.5WO3(high temperature)→2Bi(Cu 3 / 4 W 1 / 4 )O3.

[0039] The chemical reactions of BaCO3, CaCO3, ZrO2, TiO2 and Bi2O3, CuO, WO3 at high temperature are shown as follows:

[0040] 1.7(1-x)BaCO3+0.3(1-x)CaCO3+0.2(1-x)ZrO2+1.8(1-x)TiO2+xBi2O3+1.5xCuO+0.5xWO3(high temperature)→2(Ba 0.85 Ca 0.15 ) (1-x) (Zr 0.1 Ti 0.9 ) (1-x) Bi x (Cu 3 / 4 W 1 / 4 ) x O3+2(1-x)CO2.

[0041] wherein, (Ba 0.85 Ca 0.15 ) (1-x) (Zr 0.1 Ti 0.9 ) (1-x) Bi x (Cu 3 / 4 W 1 / 4 ) x O3 represents the chemical formula of the solid solution of (Ba 0.85 Ca 0.15 )(Zr 0.1 Ti 0.9 )O3 and Bi(Cu 3 / 4 W 1 / 4 )O3, the molar ratio of (Ba 0.85 Ca 0.15 )(Zr 0.1 Ti 0.9 )O3 and Bi(Cu 3 / 4W 1 / 4 )O3 is (1-x):x, and x is 0.001-0.02.

[0042] Example 1:

[0043] In step one, the molar ratio of BaCO3, CaCO3, ZrO2, TiO2 and Bi2O3, CuO, WO3 is calculated according to the molar ratio of (Ba 0.85 Ca 0.15 )(Zr 0.1 Ti 0.9 )O3 and Bi(Cu 3 / 4 W 1 / 4 )O3 is (1-x):x. Wherein x is 0.001.

[0044] In step two, the ball milling time is 12h, and anhydrous ethanol and zirconia balls are added during the ball milling. The mass ratio of the mixture, anhydrous ethanol and zirconia balls is 1:1.5:2. The drying time is 4h, and the drying temperature is 80℃. The pre-sintering temperature is 1200℃, the holding time is 4h, and the heating rate is 5℃ / min.

[0045] In step three, the ball milling time is 8h, and anhydrous ethanol and zirconia balls are added during the ball milling. The mass ratio of the main crystal phase powder, anhydrous ethanol and zirconia balls is 1:1.5:2. The drying time is 2h, and the drying temperature is 100℃. A binder with a mass concentration of 7% is added to the main crystal phase powder after drying to perform granulation, and a 60 mesh and 80 mesh sieve is used to screen the particles between 60-80 mesh for tabletting. The binder uses polyvinyl alcohol. The tabletting pressure is 8MPa.

[0046] In step three, when sintering the ceramic green body obtained after tabletting, first heat to 600℃ at a rate of 3℃ / min, and hold for 4h to remove glue, then heat to 1500℃ at the same rate, hold for 4h, and then cool to 700℃ at a rate of 5℃ / min, and naturally cool to obtain the lead-free perovskite ceramic material.

[0047] After step three, step four is further included: after polishing and cleaning the lead-free perovskite ceramic material, silver electrodes are coated on both the front and back surfaces, sintered at 600℃ for 30min to obtain the lead-free perovskite ceramic material sample.

[0048] Example 2:

[0049] In step one, the molar ratio of BaCO3, CaCO3, ZrO2, TiO2 and Bi2O3, CuO, WO3 is calculated according to the molar ratio of (Ba 0.85 Ca 0.15 )(Zr 0.1 Ti 0.9 )O3 and Bi(Cu 3 / 4 W 1 / 4The molar ratio of BaCO3, CaCO3, ZrO2, TiO2 and Bi2O3, CuO, WO3 is calculated according to the molar ratio of (1-x):x of (Ba

[0050] Illustratively, in step two, the ball milling time is 12h, and anhydrous ethanol and zirconia balls are added during ball milling, and the mass ratio of the mixture, anhydrous ethanol and zirconia balls is 1:1.5:2. The drying time is 2h, and the drying temperature is 100℃. The pre-sintering temperature is 1200℃, the holding time is 4h, and the heating rate is 5℃ / min.

[0051] Illustratively, in step three, the ball milling time is 8h, and anhydrous ethanol and zirconia balls are added during ball milling, and the mass ratio of the main crystal phase powder, anhydrous ethanol and zirconia balls is 1:1.5:2. The drying time is 4h, and the drying temperature is 80℃. A binder with a mass concentration of 7% is added to the main crystal phase powder after drying to perform granulation, and 60-80 mesh particles are screened out by using a 60 mesh and an 80 mesh sieve to perform tabletting. The binder uses polyvinyl alcohol. The tabletting pressure is 14MPa.

[0052] Illustratively, in step three, when sintering the ceramic green body obtained after tabletting, first, the temperature is raised to 600℃ at a rate of 3℃ / min, and the glue is removed by holding for 3h, then the temperature is raised to 1480℃ at the same rate, and holding for 4h, then the temperature is lowered to 700℃ at a rate of 5℃ / min, and the lead-free perovskite ceramic material is obtained after natural cooling.

[0053] Illustratively, after step three, it further includes: step four, polishing and washing the lead-free perovskite ceramic material, and coating silver electrodes on both the front and back surfaces, sintering at 600℃ for 30min to obtain a lead-free perovskite ceramic material sample.

[0054] Example 3:

[0055] Illustratively, in step one, the molar ratio of (Ba 0.85 Ca 0.15 )(Zr 0.1 Ti 0.9 )O3 and Bi(Cu 3 / 4 W 1 / 4 )O3 is calculated according to the molar ratio of (1-x):x of BaCO3, CaCO3, ZrO2, TiO2 and Bi2O3, CuO, WO3. The value of x is 0.0045.

[0056] Exemplarily, in step two, the ball milling time is 12h, and anhydrous ethanol and zirconia ball stones are added during the ball milling, and the mass ratio of the mixture, the anhydrous ethanol and the zirconia ball stones is 1:1.5:2. The drying time is 3h, and the drying temperature is 80℃. The pre-sintering temperature is 1100℃, the holding time is 5h, and the heating rate is 3℃ / min.

[0057] Exemplarily, in step three, the ball milling time is 8h, and anhydrous ethanol and zirconia ball stones are added during the ball milling, and the mass ratio of the main crystal phase powder, the anhydrous ethanol and the zirconia ball stones is 1:1.5:2. The drying time is 3h, and the drying temperature is 90℃. The main crystal phase powder after drying is added with a binder with a mass concentration of 5% for granulation, and particles between 60-80 meshes are screened out by using a 60-mesh and an 80-mesh screen for tabletting. The binder uses polyvinyl alcohol. The tabletting pressure is 16MPa.

[0058] Exemplarily, in step three, the ceramic green body obtained after tabletting is sintered by first increasing the temperature to 600℃ at a rate of 3℃ / min, holding for 2h to remove glue, then increasing the temperature to 1480℃ at the same rate, holding for 4h, and then decreasing the temperature to 700℃ at a rate of 5℃ / min, and the lead-free perovskite ceramic material is obtained after natural cooling.

[0059] Exemplarily, after step three, it further includes: step four, polishing and washing the lead-free perovskite ceramic material, coating silver electrodes on both the front and back surfaces, sintering at 600℃ for 30min, and obtaining a lead-free perovskite ceramic material sample.

[0060] Example 4:

[0061] Exemplarily, in step one, the molar ratio of (Ba 0.85 Ca 0.15 )(Zr 0.1 Ti 0.9 )O3 to Bi(Cu 3 / 4 W 1 / 4 )O3 is (1-x):x to calculate the molar ratio of BaCO3, CaCO3, ZrO2, TiO2 and Bi2O3, CuO, WO3. The value of x is 0.006.

[0062] Exemplarily, in step two, the ball milling time is 12h, and anhydrous ethanol and zirconia ball stones are added during the ball milling, and the mass ratio of the mixture, the anhydrous ethanol and the zirconia ball stones is 1:1.5:2. The drying time is 4h, and the drying temperature is 90℃. The pre-sintering temperature is 1200℃, the holding time is 5h, and the heating rate is 3℃ / min.

[0063] In the step three, the ball milling time is 8h, and anhydrous ethanol and zirconia balls are added during the ball milling. The mass ratio of the main crystal phase powder, the anhydrous ethanol and the zirconia balls is 1:1.5:2. The drying time is 4h, and the drying temperature is 80℃. The binder with a mass concentration of 6% is added to the main crystal phase powder after drying to perform granulation, and the particles between 60-80 meshes are selected by using a 60-mesh and an 80-mesh screen to perform tabletting. The binder is polyvinyl alcohol. The pressure during tabletting is 20MPa.

[0064] In the step three, the ceramic green body obtained after tabletting is sintered. Firstly, the temperature is raised to 600℃ at a rate of 3℃ / min, and the glue is removed by keeping the temperature for 3h. Then, the temperature is raised to 1460℃ at the same rate, and kept for 4h. Subsequently, the temperature is lowered to 700℃ at a rate of 5℃ / min, and the lead-free perovskite ceramic material is obtained after natural cooling.

[0065] In the step three, the ceramic green body obtained after tabletting is sintered. Firstly, the temperature is raised to 600℃ at a rate of 3℃ / min, and the glue is removed by keeping the temperature for 3h. Then, the temperature is raised to 1460℃ at the same rate, and kept for 4h. Subsequently, the temperature is lowered to 700℃ at a rate of 5℃ / min, and the lead-free perovskite ceramic material is obtained after natural cooling.

[0066] Example 5:

[0067] In the step one, the molar ratio of (Ba 0.85 Ca 0.15 )(Zr 0.1 Ti 0.9 )O3 to Bi(Cu 3 / 4 W 1 / 4 )O3 is (1-x):x to calculate the molar ratio of BaCO3, CaCO3, ZrO2, TiO2 and Bi2O3, CuO, WO3. The value of x is 0.012.

[0068] In the step two, the ball milling time is 12h, and anhydrous ethanol and zirconia balls are added during the ball milling. The mass ratio of the mixture, the anhydrous ethanol and the zirconia balls is 1:1.5:2. The drying time is 4h, and the drying temperature is 80℃. The pre-sintering temperature is 1200℃, and the keeping time is 3h. The temperature rising rate is 4℃ / min.

[0069] In the step three, the ball milling time is 8h, and anhydrous ethanol and zirconia balls are added during the ball milling. The mass ratio of the main crystal phase powder, the anhydrous ethanol and the zirconia balls is 1:1.5:2. The drying time is 4h, and the drying temperature is 80℃. The binder with a mass concentration of 6% is added to the main crystal phase powder after drying to perform granulation, and the particles between 60-80 meshes are selected by using a 60-mesh and an 80-mesh screen to perform tabletting. The binder is polyvinyl alcohol. The pressure during tabletting is 18MPa.

[0070] Exemplarily, in step three, when sintering the ceramic green body obtained after tabletting, the temperature is first raised to 600 DEG C at a rate of 3 DEG C / min, and the temperature is kept for 2h to remove the glue, then the temperature is raised to 1440 DEG C at the same rate, and the temperature is kept for 3.5h, then the temperature is lowered to 700 DEG C at a rate of 5 DEG C / min, and the lead-free perovskite ceramic material is obtained after natural cooling.

[0071] Exemplarily, after step three, step four further comprises: polishing and cleaning the lead-free perovskite ceramic material, coating silver electrodes on both front and back surfaces, sintering at 600 DEG C for 30min, and obtaining a lead-free perovskite ceramic material sample.

[0072] Embodiment 6:

[0073] Exemplarily, in step one, the molar ratio of BaCO3, CaCO3, ZrO2, TiO2 and Bi2O3, CuO, WO3 is calculated according to the molar ratio of (Ba 0.85 Ca 0.15 )(Zr 0.1 Ti 0.9 )O3 and Bi(Cu 3 / 4 W 1 / 4 )O3, which is (1-x):x. The value of x is 0.02.

[0074] Exemplarily, in step two, the ball milling time is 12h, and anhydrous ethanol and zirconia balls are added during ball milling, and the mass ratio of the mixture, anhydrous ethanol and zirconia balls is 1:1.5:2. The drying time is 4h, and the drying temperature is 80 DEG C. The pre-sintering temperature is 1000 DEG C, the holding time is 5h, and the temperature rising rate is 5 DEG C / min.

[0075] Exemplarily, in step three, the ball milling time is 8h, and anhydrous ethanol and zirconia balls are added during ball milling, and the mass ratio of the main crystal phase powder, anhydrous ethanol and zirconia balls is 1:1.5:2. The drying time is 4h, and the drying temperature is 80 DEG C. A binder with a mass concentration of 6% is added to the main crystal phase powder after drying for granulation, and 60-80 mesh particles are selected by using 60 mesh and 80 mesh sieves for tabletting. The binder is polyvinyl alcohol. The pressure during tabletting is 14MPa.

[0076] Exemplarily, in step three, when sintering the ceramic green body obtained after tabletting, the temperature is first raised to 600 DEG C at a rate of 3 DEG C / min, and the temperature is kept for 2h to remove the glue, then the temperature is raised to 1440 DEG C at the same rate, and the temperature is kept for 3.5h, then the temperature is lowered to 700 DEG C at a rate of 5 DEG C / min, and the lead-free perovskite ceramic material is obtained after natural cooling.

[0077] Exemplarily, after step three, step four is further included: polishing and cleaning the lead-free perovskite ceramic material, and then coating silver electrodes on both front and back surfaces, and sintering at 600°C for 30 min to obtain a lead-free perovskite ceramic material sample.

[0078] The piezoelectric properties d 33 coefficients of the lead-free perovskite ceramic materials provided in Examples 1 to 6 are shown in Table 1.

[0079] The piezoelectric properties d 33 coefficients of the lead-free perovskite ceramic materials provided in Examples 1 to 6 are shown in Table 1.

[0080]

[0081] Figure 2 The piezoelectric properties d 33 coefficients of the lead-free perovskite ceramic materials provided in Examples 1 to 6 are shown in Table 1.

[0082] From Table 1 and Figure 2 It can be seen that the piezoelectric properties d 33 coefficients of the lead-free perovskite ceramic materials provided in Examples 1 to 6 are shown in Table 1.

[0083] As shown in Table 1, the piezoelectric properties d Figure 3 coefficients of the lead-free perovskite ceramic material provided in Example 4 are shown in Table 1. Figure 3 It can be seen that the transmittance of the lead-free perovskite ceramic material provided in Example 4 after polarization is obviously improved relative to the transmittance before polarization, and the transmittance T after polarization can reach 30%.

[0084] As shown in Table 1, the piezoelectric properties d Figure 4 coefficients of the lead-free perovskite ceramic material provided in Example 4 are shown in Table 1.

[0085] As shown in Table 1, the piezoelectric properties d Figure 5 coefficients of the lead-free perovskite ceramic material provided in Example 4 are shown in Table 1. Figure 5 (a) is the original picture of high-angle annular dark-field imaging, according to Figure 5 (a) is the original picture of high-angle annular dark-field imaging, according to Figure 5 (a) is the original picture of high-angle annular dark-field imaging, according to Figure 5(c) refers to the lattice distortion under the coupling effect in horizontal and vertical directions, which indicates that there are local disturbances and periodic changes, forming alternating distortion strips; in addition, Figure 5 (d) it can be seen that the strain distribution in the vertical direction is deepened, which indicates that the lattice distortion is increased. Therefore, it can be seen from the strain distribution in different directions that the lead-free perovskite ceramic material provided in Example 4 has a large lattice distortion.

[0086] The application embodiment realizes the solid solution of Bi(Cu 3 / 4 W 1 / 4 )O3 into (Ba 0.85 Ca 0.15 )(Zr 0.1 Ti 0.9 )O3 by designing a preparation method, and a lead-free perovskite ceramic material is prepared. 33 The piezoelectric performance d 0.85 coefficient of the lead-free perovskite ceramic material can reach 724 pC / N, and the transmittance T after polarization can reach 30%.

[0087] The lead-free perovskite ceramic material prepared by the solid solution of (Ba 0.85 Ca 0.15 )(Zr 0.1 Ti 0.9 )O3 and Bi(Cu 3 / 4 W 1 / 4 )O3 has simple preparation process, low cost, is suitable for mass production, and does not contain lead in raw materials, belongs to an environmentally friendly ceramic material, and meets the needs of social development.

[0088] Although the preferred embodiments of the application have been described, those skilled in the art can make further changes and modifications to the embodiments once they know the basic inventive concept. Therefore, the appended claims are intended to be interpreted as including all changes and modifications falling within the scope of the application.

[0089] Obviously, those skilled in the art can make various modifications and variations to the application without departing from the spirit and scope of the application. Thus, if these modifications and variations of the application fall within the scope of the claims of the application and their equivalents, the application also intends to include these modifications and variations.

Claims

1. A method for preparing a high-transparency lead-free perovskite ceramic material, characterized in that, Includes the following steps: Step 1: Mix BaCO3, CaCO3, ZrO2, TiO2, Bi2O3, CuO, and WO3 to obtain a mixture; Step 2: The mixture is sequentially ball-milled, dried, and pre-calcined to obtain the main crystalline phase powder; Step 3: The main crystalline phase powder is ball-milled and dried in sequence, and then granulated, pressed into sheets and sintered in sequence to obtain lead-free perovskite ceramic material and polarize it. In step one, according to (Ba 0.85 Ca 0.15 (Zr) 0.1 Ti 0.9 O3 and Bi(Cu) 3 / 4 W 1 / 4 The molar ratio of O3 is (1-x):x to calculate the molar ratio of BaCO3, CaCO3, ZrO2, TiO2 and Bi2O3, CuO, WO3, where x takes the value of 0.

006.

2. The method for preparing a high-transparency lead-free perovskite ceramic material according to claim 1, characterized in that, In step two, the ball milling time is 12 hours. Anhydrous ethanol and zirconia balls are added during ball milling. The mass ratio of the mixture, anhydrous ethanol and zirconia balls is 1:1.5:

2. In step two, the drying time is 2-4 hours and the drying temperature is 80-100℃.

3. The method for preparing a high-transparency lead-free perovskite ceramic material according to claim 1, characterized in that, In step two, the preheating temperature is 1000℃-1200℃, the holding time is 3-5h, and the heating rate is 3-5℃ / min.

4. The method for preparing a high-transparency lead-free perovskite ceramic material according to claim 1, characterized in that, In step three, the ball milling time is 8 hours. Anhydrous ethanol and zirconia balls are added during ball milling. The mass ratio of main crystalline phase powder, anhydrous ethanol and zirconia balls is 1:1.5:

2. In step three, the drying time is 2-4 hours and the drying temperature is 80-100℃.

5. The method for preparing a high-transparency lead-free perovskite ceramic material according to claim 1, characterized in that, In step three, a binder with a mass concentration of 5%-7% is added to the dried main crystalline phase powder for granulation, and particles between 60-80 mesh are screened out using 60-mesh and 80-mesh sieves for tableting. The adhesive is polyvinyl alcohol; The pressure during tablet compression is 8-20 MPa.

6. The method for preparing a high-transparency lead-free perovskite ceramic material according to claim 1, characterized in that, In step three, when sintering the ceramic green body obtained after pressing, the temperature is first raised to 600℃ at a rate of 3℃ / min and held for 2-4 hours to remove the binder. Then, the temperature is raised to 1400-1500℃ at the same rate and held for 3-4 hours. Subsequently, the temperature is lowered to 700℃ at a rate of 5℃ / min and naturally cooled to obtain lead-free perovskite ceramic material.

7. A high-transparency lead-free perovskite ceramic material, characterized in that, By(Ba 0.85 Ca 0.15 (Zr) 0.1 Ti 0.9 O3 and Bi(Cu) 3 / 4 W 1 / 4 It is prepared by solid solution of O3, that is, by the preparation method of a high transparency lead-free perovskite ceramic material as described in any one of claims 1 to 6.

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