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

Abstract

The invention discloses a high-transparency lead-free perovskite ceramic material and a preparation method, and relates to the technical field of piezoelectric ceramic dielectric materials, and the method comprises the following steps: mixing BaCO3, CaCO3, ZrO2, TiO2, Bi2O3, CuO and WO3 to obtain a mixture; sequentially carrying out ball milling, drying and pre-sintering on the mixture to obtain main crystal phase powder; and sequentially carrying out ball milling and drying on the main crystal phase powder, and then sequentially carrying out granulation, tabletting and sintering to obtain the lead-free perovskite ceramic material. By designing the preparation method, Bi (Cu3 / 4W1 / 4) O3 is subjected to solid solution to (Ba0. 85Ca0. 15) (Zr0. 1Ti0. 9) O3, and the prepared lead-free perovskite ceramic material has relatively good piezoelectric property due to large lattice distortion generated in the lead-free perovskite ceramic material, and has relatively good transmittance after polarization.

Description

Technical Field

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

[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. 0.85 Ca 0.15 )(Zr 0.1 Ti 0.9 )O3) possesses high piezoelectric properties due to its numerous internal electric domains, promising promising applications in piezoelectrics and attracting considerable attention in recent years. However, pure BCZT-based ceramics suffer from low Curie temperatures, difficulty in polarization, and low transparency. Therefore, research on doped lead-free perovskite ceramics is warranted.

[0003] In the prior art, Chinese patent CN114804865A discloses a method for preparing a transparent ceramic of barium calcium zirconate titanate, which comprises the following steps: (1) preparing ingredients: the general chemical formula is xBa(Zr 0.2 Ti 0.8 )O3-(1-x) 0.5 (Ba 0.7 Ca 0.3 )TiO3, weigh the raw materials BaTiO3, ZrO2, CaCO3, and TiO2 according to the stoichiometric ratio, first add the ball milling medium into the ball mill, then add the weighed raw materials into the ball mill in sequence, and then add the liquid; (2) ball milling; (3) sand milling; (4) drying; (5) grinding and screening: (6) calcining; (7) sintering: placing the calcined powder in an SPS sintering furnace; (8) annealing; to obtain barium calcium zirconate titanate transparent ceramics.

[0004] The ceramic material prepared by the above-mentioned prior art has a transmittance of 10.1% at a thickness of 0.6 mm, which is relatively low, and the piezoelectric performance needs to be improved. Summary of the Invention

[0005] The present application provides a high-transparency lead-free perovskite ceramic material and a preparation method to solve the problem that the transmittance of existing piezoelectric ceramic dielectric materials is low and the piezoelectric performance needs to be improved.

[0006] In one aspect, the present application provides a method for preparing a high-transparency lead-free perovskite ceramic material, comprising the following steps: Step 1: Mix BaCO3, CaCO3, ZrO2, TiO2 and Bi2O3, CuO, and WO3 to obtain a mixture.

[0007] Step 2: ball milling, drying and pre-calcining the mixture in sequence to obtain main crystal phase powder.

[0008] Step three: ball milling and drying the main crystalline phase powder in sequence, and then granulating, tableting, and sintering in sequence to obtain a lead-free perovskite ceramic material.

[0009] In a possible implementation, in step 1, according to (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 to calculate the molar ratio of BaCO3, CaCO3, ZrO2, TiO2 and Bi2O3, CuO, WO3, where the value of x is 0.001-0.02.

[0010] In a possible implementation, in step 2, the ball milling time is 12 hours, anhydrous ethanol and zirconia balls are added during the ball milling, and the mass ratio of the mixture, anhydrous ethanol, and zirconia balls is 1:1.5:2.

[0011] In step 2, the drying time is 2-4 hours and the drying temperature is 80-100°C.

[0012] In a possible implementation, in step 2, the pre-firing temperature is 1000° C.-1200° C., the holding time is 3-5 hours, and the heating rate is 3-5° C. / min.

[0013] In a possible implementation, in step three, the ball milling time is 8 hours, anhydrous ethanol and zirconia balls are added during the ball milling, and the mass ratio of the main crystal phase powder, anhydrous ethanol, and zirconia balls is 1:1.5:2.

[0014] In step 3, the drying time is 2-4 hours and the drying temperature is 80-100°C.

[0015] In one possible implementation, in step three, a binder having a mass concentration of 5%-7% is added to the dried main crystal phase powder for granulation, and 60-mesh and 80-mesh sieves are used to screen out particles between 60 and 80 meshes for tableting.

[0016] The binder is polyvinyl alcohol.

[0017] The pressure during tableting is 8-20MPa.

[0018] In one possible implementation, in step three, when sintering the ceramic green body obtained after tableting, the temperature is first raised to 600°C at a rate of 3°C / min, kept warm for 2-4 hours to remove the binder, then raised to 1400-1500°C at the same rate, kept warm for 3-4 hours, and then cooled to 700°C at a rate of 5°C / min. After natural cooling, a lead-free perovskite ceramic material is obtained.

[0019] On the other hand, the present application provides a high transparency lead-free perovskite ceramic material, comprising (Ba 0.85 Ca 0.15 )(Zr 0.1 Ti 0.9 )O3 and Bi(Cu 3 / 4 W 1 / 4 )O3 solid solution, that is, it is prepared by the above-mentioned preparation method of a high-transparency lead-free perovskite ceramic material.

[0020] The high-transparency lead-free perovskite ceramic material and preparation method in this application have the following advantages: By designing the preparation method, Bi(Cu 3 / 4 W 1 / 4 )O3 solid solution to (Ba 0.85 Ca 0.15 )(Zr 0.1 Ti 0.9 )O3, the lead-free perovskite ceramic material produced has a large lattice distortion inside, which can obtain good piezoelectric properties and has relatively good transmittance after polarization. 33 The coefficient can reach 724 pC / N, and the transmittance T after polarization can reach 30%.

[0021] Proposed by (Ba 0.85 Ca 0.15 )(Zr 0.1 Ti 0.9 )O3 and Bi(Cu 3 / 4 W 1 / 4 )O3 solid solution lead-free perovskite ceramic material, the preparation process is simple, the cost is low, suitable for mass production, and the raw materials do not contain lead, which is an environmentally friendly ceramic material that meets the needs of social development. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are only some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without any creative work.

[0023] Figure 1 A schematic flow chart of a method for preparing a high-transparency lead-free perovskite ceramic material provided in an embodiment of the present application; Figure 2 The piezoelectric properties of the lead-free perovskite ceramic materials provided in Examples 1 to 6 of the present application are as follows: 33 Coefficient fitting curve graph; Figure 3 This is a transmittance curve of the lead-free perovskite ceramic material provided in Example 4 of the present application before and after polarization; Figure 4 Comparison of visible light photographs of the lead-free perovskite ceramic material provided in Example 4 of the present application before and after polarization; Figure 5 Schematic diagram of strain field analysis of high-angle annular dark field imaging of the lead-free perovskite ceramic material provided in Example 4 of the present application. DETAILED DESCRIPTION

[0024] The following will be combined with the drawings in the embodiments of this application to clearly and completely describe the technical solutions in the embodiments of this application. Obviously, the embodiments described are only part of the embodiments of this application, not all of the embodiments. Based on the embodiments in this application, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of this application.

[0025] like Figure 1 As shown, the embodiment of the present application provides a method for preparing a high-transparency lead-free perovskite ceramic material, comprising the following steps: Step 1: Mix BaCO3, CaCO3, ZrO2, TiO2 and Bi2O3, CuO, and WO3 to obtain a mixture.

[0026] Step 2: ball milling, drying and pre-calcining the mixture in sequence to obtain main crystal phase powder.

[0027] Step three: ball milling and drying the main crystalline phase powder in sequence, and then granulating, tableting, and sintering in sequence to obtain a lead-free perovskite ceramic material.

[0028] Specifically, the chemical reactions of BaCO3, CaCO3, ZrO2, and TiO2 at high temperatures are as follows: 0.85BaCO3+0.15CaCO3+0.1ZrO2+0.9TiO2 (high temperature) → (Ba 0.85 Ca 0.15 )(Zr 0.1 Ti 0.9 )O3+CO2.

[0029] The chemical reactions of Bi2O3, CuO and WO3 at high temperatures are as follows: Bi2O3+1.5CuO+0.5WO3 (high temperature)→2Bi(Cu 3 / 4 W 1 / 4 )O3.

[0030] The chemical reactions of BaCO3, CaCO3, ZrO2, TiO2 and Bi2O3, CuO, WO3 at high temperatures are as follows: 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.

[0031] Among them, (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 means (Ba 0.85 Ca 0.15 )(Zr 0.1 Ti 0.9 )O3 and Bi(Cu 3 / 4 W 1 / 4 )O3 solid solution chemical formula, (Ba 0.85 Ca 0.15 )(Zr 0.1 Ti 0.9 )O3 and Bi(Cu 3 / 4W 1 / 4 )The molar ratio of O3 is (1-x):x, and the value of x is 0.001-0.02.

[0032] Example 1: For example, in step 1, according to (Ba 0.85 Ca 0.15 )(Zr 0.1 Ti 0.9 )O3 and Bi(Cu 3 / 4W 1 / 4 The molar ratios of BaCO3, CaCO3, ZrO2, TiO2, Bi2O3, CuO, and WO3 are calculated using the molar ratio of )O3 as (1-x):x, where x is 0.001.

[0033] For example, in step 2, the ball milling time is 12 hours, and anhydrous ethanol and zirconia balls are added during the ball milling process. The mass ratio of the mixture, anhydrous ethanol, and zirconia balls is 1:1.5:2. The drying time is 4 hours, and the drying temperature is 80°C. The pre-calcination temperature is 1200°C, the holding time is 4 hours, and the heating rate is 5°C / min.

[0034] For example, in step 3, the ball milling time is 8 hours, and anhydrous ethanol and zirconia balls are added during ball milling. The mass ratio of the main crystalline phase powder, anhydrous ethanol, and zirconia balls is 1:1.5:2. The drying time is 2 hours, and the drying temperature is 100°C. A binder with a mass concentration of 7% is added to the dried main crystalline phase powder for granulation, and 60-mesh and 80-mesh sieves are used to screen out particles between 60 and 80 mesh for tableting. The binder is polyvinyl alcohol. The pressure during tableting is 8 MPa.

[0035] For example, in step three, when sintering the ceramic green body obtained after tableting, the temperature is first raised to 600°C at a rate of 3°C / min, kept warm for 4 hours to remove the binder, then raised to 1500°C at the same rate, kept warm for 4 hours, and then cooled to 700°C at a rate of 5°C / min. After natural cooling, a lead-free perovskite ceramic material is obtained.

[0036] Exemplarily, step three also includes: step four, polishing and cleaning the lead-free perovskite ceramic material, coating silver electrodes on both sides, and sintering at 600° C. for 30 minutes to obtain a lead-free perovskite ceramic material sample.

[0037] Example 2: For example, in step 1, 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 ratios of BaCO3, CaCO3, ZrO2, TiO2, Bi2O3, CuO, and WO3 are calculated using the molar ratio of O3 as (1-x):x, where x is 0.003.

[0038] For example, in step 2, the ball milling time is 12 hours, and anhydrous ethanol and zirconia balls are added during the ball milling process. The mass ratio of the mixture, anhydrous ethanol, and zirconia balls is 1:1.5:2. The drying time is 2 hours, and the drying temperature is 100°C. The pre-calcination temperature is 1200°C, the holding time is 4 hours, and the heating rate is 5°C / min.

[0039] For example, in step three, the ball milling time is 8 hours, and anhydrous ethanol and zirconia balls are added during ball milling. The mass ratio of the main crystalline phase powder, anhydrous ethanol, and zirconia balls is 1:1.5:2. The drying time is 4 hours, and the drying temperature is 80°C. A binder with a mass concentration of 7% is added to the dried main crystalline phase powder for granulation, and 60-mesh and 80-mesh sieves are used to screen out particles between 60 and 80 mesh for tableting. The binder is polyvinyl alcohol. The pressure during tableting is 14 MPa.

[0040] For example, in step three, when sintering the ceramic green body obtained after tableting, the temperature is first raised to 600°C at a rate of 3°C / min, kept warm for 3 hours to remove the binder, then raised to 1480°C at the same rate, kept warm for 4 hours, and then cooled to 700°C at a rate of 5°C / min. After natural cooling, a lead-free perovskite ceramic material is obtained.

[0041] Exemplarily, step three also includes: step four, polishing and cleaning the lead-free perovskite ceramic material, coating silver electrodes on both sides, and sintering at 600° C. for 30 minutes to obtain a lead-free perovskite ceramic material sample.

[0042] Example 3: For example, in step 1, 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 ratios of BaCO3, CaCO3, ZrO2, TiO2, Bi2O3, CuO, and WO3 are calculated using the molar ratio of O3 as (1-x):x, where x is 0.0045.

[0043] For example, in step 2, the ball milling time is 12 hours, and anhydrous ethanol and zirconia balls are added during the ball milling process. The mass ratio of the mixture, anhydrous ethanol, and zirconia balls is 1:1.5:2. The drying time is 3 hours, and the drying temperature is 80°C. The pre-calcination temperature is 1100°C, the holding time is 5 hours, and the heating rate is 3°C / min.

[0044] For example, in step 3, the ball milling time is 8 hours, and anhydrous ethanol and zirconia balls are added during ball milling. The mass ratio of the main crystalline phase powder, anhydrous ethanol, and zirconia balls is 1:1.5:2. The drying time is 3 hours, and the drying temperature is 90°C. A binder with a mass concentration of 5% is added to the dried main crystalline phase powder for granulation, and 60-mesh and 80-mesh sieves are used to screen out particles between 60 and 80 mesh for tableting. The binder is polyvinyl alcohol. The pressure during tableting is 16 MPa.

[0045] For example, in step three, when sintering the ceramic green body obtained after tableting, the temperature is first raised to 600°C at a rate of 3°C / min, kept warm for 2 hours to remove the binder, then raised to 1480°C at the same rate, kept warm for 4 hours, and then cooled to 700°C at a rate of 5°C / min. After natural cooling, a lead-free perovskite ceramic material is obtained.

[0046] Exemplarily, step three also includes: step four, polishing and cleaning the lead-free perovskite ceramic material, coating silver electrodes on both sides, and sintering at 600° C. for 30 minutes to obtain a lead-free perovskite ceramic material sample.

[0047] Example 4: For example, in step 1, 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 ratios of BaCO3, CaCO3, ZrO2, TiO2, Bi2O3, CuO, and WO3 are calculated using the molar ratio of )O3 as (1-x):x, where x is 0.006.

[0048] For example, in step 2, the ball milling time is 12 hours, and anhydrous ethanol and zirconia balls are added during the ball milling process. The mass ratio of the mixture, anhydrous ethanol, and zirconia balls is 1:1.5:2. The drying time is 4 hours, and the drying temperature is 90°C. The pre-calcination temperature is 1200°C, the holding time is 5 hours, and the heating rate is 3°C / min.

[0049] For example, in step 3, the ball milling time is 8 hours, and anhydrous ethanol and zirconia balls are added during ball milling. The mass ratio of the main crystalline phase powder, anhydrous ethanol, and zirconia balls is 1:1.5:2. The drying time is 4 hours, and the drying temperature is 80°C. A binder with a mass concentration of 6% is added to the dried main crystalline phase powder for granulation, and 60-mesh and 80-mesh sieves are used to screen out particles between 60 and 80 mesh for tableting. The binder is polyvinyl alcohol. The pressure during tableting is 20 MPa.

[0050] For example, in step three, when sintering the ceramic green body obtained after tableting, the temperature is first raised to 600°C at a rate of 3°C / min, kept warm for 3 hours to remove the binder, then raised to 1460°C at the same rate, kept warm for 4 hours, and then cooled to 700°C at a rate of 5°C / min. After natural cooling, a lead-free perovskite ceramic material is obtained.

[0051] Exemplarily, step three also includes: step four, polishing and cleaning the lead-free perovskite ceramic material, coating silver electrodes on both sides, and sintering at 600° C. for 30 minutes to obtain a lead-free perovskite ceramic material sample.

[0052] Example 5: For example, in step 1, 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 ratios of BaCO3, CaCO3, ZrO2, TiO2, Bi2O3, CuO, and WO3 are calculated using the molar ratio of )O3 as (1-x):x, where x is 0.012.

[0053] For example, in step 2, the ball milling time is 12 hours, and anhydrous ethanol and zirconia balls are added during the ball milling process. The mass ratio of the mixture, anhydrous ethanol, and zirconia balls is 1:1.5:2. The drying time is 4 hours, and the drying temperature is 80°C. The pre-calcination temperature is 1200°C, the holding time is 3 hours, and the heating rate is 4°C / min.

[0054] For example, in step three, the ball milling time is 8 hours, and anhydrous ethanol and zirconia balls are added during ball milling. The mass ratio of the main crystalline phase powder, anhydrous ethanol, and zirconia balls is 1:1.5:2. The drying time is 4 hours, and the drying temperature is 80°C. A binder with a mass concentration of 6% is added to the dried main crystalline phase powder for granulation, and 60-mesh and 80-mesh sieves are used to screen out particles between 60 and 80 mesh for tableting. The binder is polyvinyl alcohol. The pressure during tableting is 18 MPa.

[0055] For example, in step three, when sintering the ceramic green body obtained after tableting, the temperature is first raised to 600°C at a rate of 3°C / min, kept warm for 2 hours to remove the binder, then raised to 1440°C at the same rate, kept warm for 3.5 hours, and then cooled to 700°C at a rate of 5°C / min. After natural cooling, a lead-free perovskite ceramic material is obtained.

[0056] Exemplarily, step three also includes: step four, polishing and cleaning the lead-free perovskite ceramic material, coating silver electrodes on both sides, and sintering at 600° C. for 30 minutes to obtain a lead-free perovskite ceramic material sample.

[0057] Example 6: For example, in step 1, 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 ratios of BaCO3, CaCO3, ZrO2, TiO2, Bi2O3, CuO, and WO3 are calculated using the molar ratio of )O3 as (1-x):x, where x is 0.02.

[0058] For example, in step 2, the ball milling time is 12 hours, and anhydrous ethanol and zirconia balls are added during the ball milling process. The mass ratio of the mixture, anhydrous ethanol, and zirconia balls is 1:1.5:2. The drying time is 4 hours, and the drying temperature is 80°C. The pre-calcination temperature is 1000°C, the holding time is 5 hours, and the heating rate is 5°C / min.

[0059] For example, in step 3, the ball milling time is 8 hours, and anhydrous ethanol and zirconia balls are added during ball milling. The mass ratio of the main crystalline phase powder, anhydrous ethanol, and zirconia balls is 1:1.5:2. The drying time is 4 hours, and the drying temperature is 80°C. A binder with a mass concentration of 6% is added to the dried main crystalline phase powder for granulation, and 60-mesh and 80-mesh sieves are used to screen out particles between 60 and 80 mesh for tableting. The binder is polyvinyl alcohol. The pressure during tableting is 14 MPa.

[0060] For example, in step three, when sintering the ceramic green body obtained after tableting, the temperature is first raised to 600°C at a rate of 3°C / min, kept warm for 2 hours to remove the binder, then raised to 1400°C at the same rate, kept warm for 3 hours, and then cooled to 700°C at a rate of 5°C / min. After natural cooling, a lead-free perovskite ceramic material is obtained.

[0061] Exemplarily, step three also includes: step four, polishing and cleaning the lead-free perovskite ceramic material, coating silver electrodes on both sides, and sintering at 600° C. for 30 minutes to obtain a lead-free perovskite ceramic material sample.

[0062] Table 1 shows the piezoelectric properties of the lead-free perovskite ceramic materials provided in Examples 1 to 6. 33 coefficient: Table 1 Piezoelectric properties of the lead-free perovskite ceramic materials provided by Examples 1 to 6 33 coefficient

[0063] Figure 2 The piezoelectric properties of the lead-free perovskite ceramic materials provided in Examples 1 to 6 of the present application are as follows: 33 Coefficient fitting curve plot.

[0064] From Table 1 and Figure 2 It can be seen that the piezoelectric performance of the lead-free perovskite ceramic material of this application is 33 The coefficient can reach up to 724 pC / N, corresponding to Example 4.

[0065] like Figure 3 The figure shows the transmittance curves of the lead-free perovskite ceramic material provided in Example 4 before and after polarization, wherein the poled curve is the transmittance curve after polarization and the unpoled curve is the transmittance curve before polarization. Figure 3 It can be seen that the transmittance of the lead-free perovskite ceramic material provided in Example 4 after polarization is significantly improved compared with the transmittance before polarization, and the transmittance T after polarization can reach 30%.

[0066] like Figure 4 The figure shows a comparison of visible light photographs of the lead-free perovskite ceramic material provided in Example 4 before and after polarization. The visible light photograph of the 0.3 mm thick lead-free perovskite ceramic material provided in Example 4 after polarization is obviously clearer than the visible light photograph before polarization.

[0067] like Figure 5 Shown is a schematic diagram of strain field analysis of high-angle annular dark field imaging of the lead-free perovskite ceramic material provided in Example 4. Figure 5 (a) is the original image of high-angle annular dark field imaging, according to Figure 5 (a) Strain field analysis of the lead-free perovskite ceramic material of Example 4, where the rightmost color bar indicates tensile strain in red and compressive strain in blue. Figure 5 (b) refers to the strain in the horizontal direction, from which it can be seen that there is non-uniform strain in the horizontal direction; Figure 5 (c) refers to the lattice distortion under the coupling of horizontal and vertical directions, indicating the existence of local perturbations and periodic changes, forming alternating distortion stripes; in addition, Figure 5 (d) shows the strain distribution in the vertical direction. The darkening of the color indicates the increase in lattice distortion. Therefore, the strain distribution in different directions clearly shows that the lead-free perovskite ceramic material provided by Example 4 has a large lattice distortion.

[0068] The present invention realizes the conversion of Bi(Cu) into 3 / 4 W 1 / 4 )O3 solid solution to (Ba0.85 Ca 0.15 )(Zr 0.1 Ti 0.9 )O3, the lead-free perovskite ceramic material produced has a large lattice distortion inside, which can obtain good piezoelectric properties and has relatively good transmittance after polarization. 33 The coefficient can reach 724 pC / N, and the transmittance T after polarization can reach 30%.

[0069] Proposed by (Ba 0.85 Ca 0.15 )(Zr 0.1 Ti 0.9 )O3 and Bi(Cu 3 / 4 W 1 / 4 )O3 solid solution lead-free perovskite ceramic material, the preparation process is simple, the cost is low, suitable for mass production, and the raw materials do not contain lead, which is an environmentally friendly ceramic material that meets the needs of social development.

[0070] Although the preferred embodiments of the present application have been described, those skilled in the art may make additional changes and modifications to these embodiments once they have learned the basic creative concept. Therefore, the appended claims are intended to be interpreted as including the preferred embodiments and all changes and modifications that fall within the scope of the present application.

[0071] Obviously, those skilled in the art may make various changes and modifications to this application without departing from the spirit and scope of this application. Thus, if these modifications and variations of this application fall within the scope of the claims of this application and their equivalents, this application is intended to include these modifications and variations.

Claims

1. A method for preparing a high-transparency lead-free perovskite ceramic material, characterized in that: The following steps are involved: Step 1, mixing BaCO3, CaCO3, ZrO2, TiO2 and Bi2O3, CuO, and WO3 to obtain a mixture; Step 2: ball milling, drying and pre-calcining the mixture in sequence to obtain a main crystal phase powder; Step three: ball milling and drying the main crystalline phase powder in sequence, and then granulating, tableting, and sintering in sequence to obtain a lead-free perovskite ceramic material.

2. The method for preparing a high-transparency lead-free perovskite ceramic material according to claim 1, characterized in that: In step 1, follow (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 to calculate the molar ratio of BaCO3, CaCO3, ZrO2, TiO2 and Bi2O3, CuO, WO3, where the value of x is 0.001-0.

02.

3. The method for preparing a high-transparency lead-free perovskite ceramic material according to claim 1, characterized in that: In step 2, the ball milling time is 12 hours, and anhydrous ethanol and zirconia balls are added during the ball milling, and the mass ratio of the mixture, anhydrous ethanol, and zirconia balls is 1:1.5:2; In step 2, the drying time is 2-4 hours and the drying temperature is 80-100°C.

4. The method for preparing a high-transparency lead-free perovskite ceramic material according to claim 1, characterized in that: In step 2, the pre-firing temperature is 1000°C-1200°C, the holding time is 3-5h, and the heating rate is 3-5°C / min.

5. The method for preparing a high-transparency lead-free perovskite ceramic material according to claim 1, characterized in that: In step 3, the ball milling time is 8 hours, 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; In step 3, the drying time is 2-4 hours and the drying temperature is 80-100°C.

6. The method for preparing a high-transparency lead-free perovskite ceramic material according to claim 1, characterized in that: In step 3, a binder having a mass concentration of 5% to 7% is added to the dried main crystal phase powder for granulation, and 60-mesh and 80-mesh sieves are used to screen out particles between 60 and 80 meshes for tableting; The binder is polyvinyl alcohol; The pressure during tableting is 8-20MPa.

7. 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 tableting, the temperature is first raised to 600°C at a rate of 3°C / min, kept warm for 2-4 hours to remove the binder, then raised to 1400-1500°C at the same rate, kept warm for 3-4 hours, and then cooled to 700°C at a rate of 5°C / min. After natural cooling, a lead-free perovskite ceramic material is obtained.

8. 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 )O3 solid solution, that is, it is prepared by the preparation method of a high-transparency lead-free perovskite ceramic material as described in any one of claims 1 to 7.

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