Lead manganese antimonate-lead indium niobate-lead zirconate titanate piezoelectric ceramic material and method

Abstract

The invention belongs to the technical field of piezoelectric ceramics, and particularly relates to a lead manganese antimonate-lead indium niobate-lead zirconate titanate piezoelectric ceramic material and a method. The chemical general formula of the material composition is as follows: 0.05 Pb (Mn < 1 / 3 > Sb < 2 / 3 >)] O < 3-0.92 > Pb (Zr < x > Ti < 1-x >)] O < 3-0.03 > Pb (In < 1 / 3 > Nb < 2 / 3 >)] O < 3 + y wt% Cu < O > and z wt% Fe < 2 > O < 3 >, wherein x is equal to 0.5 to 0.6, y is equal to 0.05 to 2, and z is equal to 0.05 to 3. The piezoelectric ceramic material is prepared from the following raw materials: Pb3O4, TiO2, ZrO2, MnO2, Nb2O5, In2O3, Sb2O3, CuO and Fe2O3. The piezoelectric ceramic has relatively high piezoelectric property d33 and also has relatively high mechanical quality factor.

Description

Technical Field

[0001] This invention belongs to the field of piezoelectric ceramic technology, and specifically relates to a lead manganese antimonate-lead indium niobate-lead zirconate titanate piezoelectric ceramic material and method. Background Technology

[0002] With technological advancements, the applications of piezoelectric materials are becoming increasingly diverse. The performance of conventional piezoelectric ceramic materials is gradually failing to meet market demands, necessitating the design of novel piezoelectric ceramics. For piezoelectric ceramic pumps, the piezoelectric ceramics require a large amplitude to meet flow requirements, necessitating high piezoelectric performance and an electromechanical coupling coefficient. However, long-term operation demands low dielectric loss. Currently, the piezoelectric ceramics used in liquid cooling systems for piezoelectric pumps suffer from severe heat generation. Therefore, it is necessary to design a piezoelectric ceramic material that possesses high piezoelectric performance and an electromechanical coupling coefficient, while also exhibiting low dielectric loss.

[0003] In view of the above requirements, it is of great significance to conduct in-depth research on the composition, structure and properties of lead manganese antimonate-lead indium niobate-zirconium titanate materials, and to explore a high-power piezoelectric ceramic material through the design and development of component doping, phase structure and preparation process. Summary of the Invention

[0004] The purpose of this invention is to provide a lead manganese antimonate-lead indium niobate-lead zirconate titanate piezoelectric ceramic material and method. This invention solves the problem of limited performance of conventional P-4 and P-8 piezoelectric materials and meets the market demand for high performance and low loss of piezoelectric ceramics, thereby providing a low-loss, high-performance lead manganese antimonate-lead indium niobate-lead zirconate titanate piezoelectric ceramic material.

[0005] To address the aforementioned technical problems, this invention provides a lead manganese antimonate-lead indium niobate-lead zirconate titanate piezoelectric ceramic material, the chemical formula of which is expressed as follows:

[0006] 0.05Pb(Mn 1 / 3 Sb 2 / 3 )]O3-0.92Pb(Zr x Ti (1-x) O3-0.03Pb(In) 1 / 3 Nb 2 / 3 )]O3+ywt%CuO+zwt%Fe2O3; where x=0.5~0.6, y=0.05~2, z=0.05~3.

[0007] Preferably, x = 0.53 to 0.55, y = 0.25 to 1.5, and z = 0.5.

[0008] Preferably, the raw materials for preparing the piezoelectric ceramic material include Pb3O4, TiO2, ZrO2, MnO2, Nb2O5, In2O3, Sb2O3, CuO, and Fe2O3.

[0009] This invention also provides a method for preparing a lead manganese antimonate-lead indium niobate-lead zirconate titanate piezoelectric ceramic material, comprising:

[0010] Step S1: Ingredient mixing; Weigh the raw materials according to the general stoichiometric ratio, and mix and ball mill them using a mixer. The initial mixing time is 4h to 12h.

[0011] Step S2: Pre-calcination; The powder obtained in step S1 is mixed with a small amount of deionized water, dry-pressed into blocks, placed in a crucible, and then pre-calcined in a muffle furnace to obtain pre-calcined powder, which is then coarsely crushed.

[0012] Step S3: Secondary ball milling granulation; The powder coarsely crushed in step S2 is ball-milled for 24 hours, dried, and then granulated by adding a 7wt%–10wt% polyvinyl alcohol solution, followed by sieving.

[0013] Step S4: Molding; The powder sieved in step S3 is pressed into tablets using a tablet press to prepare ceramic blanks of a specific shape;

[0014] Step S5: Debinding; The ceramic blank obtained in step S4 is placed in a muffle furnace for debinding to obtain a debinded ceramic blank. The debinding temperature is 550℃ and the debinding holding time is 2h.

[0015] Step S6: Sintering; The ceramic blank obtained in step S5 after debinding is placed in a muffle furnace, covered with zirconium dioxide powder for burial and firing, and then naturally cooled to room temperature to obtain ceramic sheets.

[0016] Preferably, in step S2, the pre-firing heating rate is 3℃ / min to 6℃ / min, the pre-firing temperature is 800℃ to 850℃, and the pre-firing holding time is 2h.

[0017] Preferably, the pre-firing temperature is 820°C.

[0018] Preferably, in step S6, the sintering temperature rise and fall parameters include: rising to 1000℃~1100℃ at a rising rate of 3℃ / min~5℃ / min, holding for 1h, then rising to 1100℃~1280℃ at a rising rate of 2℃ / min~3℃ / min, holding for 2h~3h, and after holding, cooling down to 800℃ at a cooling rate of 3℃ / min~10℃ / min, and then naturally cooling to room temperature.

[0019] Preferably, after step S6, the method further includes:

[0020] Step S7: Polishing; Polish the ceramic sheet obtained in step S6, and then perform ultrasonic cleaning and drying.

[0021] Step S8: Silver electrode firing; After drying the ceramic sheet in step S7, brush a silver electrode onto the surface that needs to be polarized, and then place it in a muffle furnace to fire silver to obtain a silver-plated ceramic sheet.

[0022] Step S9: Polarization; The ceramic sheet obtained in step S8 is polarized. The polarization process is as follows: the electric field strength is 3kv / mm to 4kv / mm, the polarization temperature is 120℃, and the polarization time is 10min to 30min.

[0023] Preferably, in step S8, the silver is heated to 750°C to 850°C at a rate of 3°C / min to 10°C / min, and held at this temperature for 20 min to 40 min.

[0024] Compared with the prior art, the present invention has the following beneficial effects:

[0025] This invention optimizes the performance of piezoelectric ceramics through multi-material composite and B-site doping methods, achieving a mechanical quality factor of 1300 while also possessing d... 33 With a piezoelectric property of ~380 pC / N and a dielectric loss of 0.3%, it boasts a mechanical quality factor Q of ~81 piezoelectric ceramics. m ~1200, piezoelectric properties d 33 The piezoelectric ceramic of this invention exhibits a significant improvement of ~220 pC / N. Compared with the traditional P4 and P8 series piezoelectric ceramics which have a sintering temperature of 1280℃-1300℃, this system has a sintering temperature of only 1100℃-1150℃, resulting in a significant reduction in production costs. Detailed Implementation

[0026] The present invention will be further described in detail below with reference to specific embodiments. The advantages and features of the present invention will become clearer from the following description.

[0027] Example 1

[0028] An embodiment of the present invention provides a lead manganese antimonate-lead indium niobate-lead zirconate titanate piezoelectric ceramic material, the composition of which is represented by the general chemical formula:

[0029] 0.0.05Pb(Mn 1 / 3 Sb 2 / 3 )]O3-0.92Pb(Zr x Ti (1-x) O3-0.03Pb(In) 1 / 3 Nb 2 / 3)]O3+ywt%CuO+zwt%Fe2O3; where x=0.53, y=0.25, z=0.5.

[0030] Specifically, the preparation methods include the following:

[0031] S1: Weigh the ingredients according to the general chemical formula, then mix them using a mixer, and finally dry them.

[0032] S2: The dried powder is mixed with a small amount of water and pressed into blocks. The powder is then pre-fired in a muffle furnace at a temperature of 800℃ for 2 hours. After pre-firing, the powder is coarsely crushed to obtain pre-fired powder.

[0033] S3: The powder obtained in S2 is ball-milled a second time for 24 hours. After drying, the powder is granulated by adding a polyvinyl alcohol solution (8 wt%).

[0034] S4: The powder obtained in step S3 is pressed into tablets using a tablet press to form a ceramic blank.

[0035] S5: The green body obtained in S4 is placed in a muffle furnace for debinding. The debinding temperature is 550℃ and the debinding holding time is 2h. Then the debinded ceramic is obtained.

[0036] S6: Place the debinding ceramic obtained in S5 into a muffle furnace, spread zirconium dioxide powder between the ceramic layers, and sinter with the following heating and cooling regime: heat up to 1000℃ at a heating rate of 3℃ / min, hold for 1 hour, then heat up to 1140℃ at a heating rate of 2℃ / min, hold for 2 hours, and after holding, cool down to 800℃ at a cooling rate of 4℃ / min, and then cool naturally to room temperature to obtain ceramic sheets.

[0037] S7: The ceramic obtained in S6 is machined to form the designed shape and then cleaned.

[0038] S8: Apply a silver electrode to the ceramic surface that needs to be polarized using S7, and then place it in a muffle furnace to burn the silver. The burning process is as follows: raise the temperature to 800℃ at a rate of 3℃ / min, and hold at this temperature for 30min. The resulting silver-coated ceramic sheet is obtained.

[0039] S9: The ceramic obtained in S8 was subjected to silicone oil polarization at a polarization voltage of 4 kV / mm, a polarization temperature of 120℃, and a polarization time of 15 min. After polarization, it was cleaned. The ceramic was then tested after being left to stand for 24 hours.

[0040] Example 2

[0041] The only difference between this embodiment of the invention and Embodiment 1 described above is that its general chemical formula is 0.0.05Pb(Mn)1 / 3Sb 2 / 3 )]O3-0.92Pb(Zr x Ti (1-x) O3-0.03Pb(In) 1 / 3 Nb 2 / 3 The composition of the material is represented by O3+ywt%CuO+zwt%Fe2O3, where x=0.54, y=0.25, and z=0.5.

[0042] Example 3

[0043] The only difference between this embodiment of the invention and Embodiment 1 described above is that its general chemical formula is 0.0.05Pb(Mn) 1 / 3Sb 2 / 3 )]O3-0.92Pb(Zr x Ti (1-x) O3-0.03Pb(In) 1 / 3 Nb 2 / 3 The composition of the material is represented by ]O3+ywt%CuO+zwt%Fe2O3, where x=0.55, y=0.25, and z=0.5.

[0044] Example 4

[0045] The only difference between this embodiment of the invention and Embodiment 1 described above is that its general chemical formula is 0.05Pb(Mn) 1 / 3Sb 2 / 3 )]O3-0.92Pb(Zr 0.52 Ti 0.48 O3-0.03Pb(In) 1 / 3 Nb 2 / 3 )]O3+ywt%CuO+0.5wt%Fe2O3, where y=0.5.

[0046] Example 5

[0047] The only difference between this embodiment of the invention and Embodiment 1 described above is that its general chemical formula is 0.05Pb(Mn) 1 / 3Sb 2 / 3 )]O3-0.92Pb(Zr 0.52 Ti 0.48 O3-0.03Pb(In) 1 / 3 Nb 2 / 3 )]O3+ywt%CuO+0.5wt%Fe2O3, where y=1.

[0048] Example 6

[0049] The only difference between this embodiment of the invention and Embodiment 1 described above is that its general chemical formula is 0.05Pb(Mn) 1 / 3Sb 2 / 3 )]O3-0.92Pb(Zr 0.52 Ti 0.48 O3-0.03Pb(In) 1 / 3 Nb 2 / 3 )]O3+ywt%CuO+0.5wt%Fe2O3, where y=1.5.

[0050] The electrical performance test results of Examples 1 to 3 are shown in Table 1 below.

[0051] Table 1. Data on piezoelectric and dielectric properties.

[0052] Example Components <![CDATA[d 33 (pC / N)]]> tanδ kp <![CDATA[Q m ]]> Tc (°C) Example 1 x＝0.53 353 0.35％ 0.57 1230 314 Example 2 x＝0.54 380 0.30％ 0.58 1311 308 Example 3 x＝0.55 371 0.41％ 0.58 1108 303

[0053] The electrical performance test results of Examples 4 to 6 above are shown in Table 2 below.

[0054] Table 2. Data on piezoelectric and dielectric properties.

[0055] Example Components <![CDATA[d 33 (pC / N)]]> tanδ kp <![CDATA[Q m ]]> Tc (°C) Example 4 y＝0.5 340 0.35％ 0.58 1230 303 Example 5 y＝1 350 0.30％ 0.60 1260 302 Example 6 y＝1.5 370 0.33％ 0.60 920 300

[0056] In summary, this invention designs a lead manganese antimonate-lead indium niobate-lead zirconate titanate piezoelectric ceramic material with the molecular formula 0.05Pb(Mn) 1 / 3 Sb 2 / 3 )]O3-0.92Pb(Zr x Ti (1-x) O3-0.03Pb(In) 1 / 3 Nb 2 / 3 The composition of the material is represented by O3+ywt%CuO+zwt%Fe2O3, where x = 0.50–0.6, y = 0.05–2, and z = 0.05–3. Solid-state sintering is used in the preparation process, with a pre-firing temperature of 800–850℃ and a sintering temperature of 1100–1150℃. Through the control of various parameters, this material can achieve a high mechanical quality factor Q. m ~1311, a relatively good piezoelectric coefficient d 33 ~380 pC / N. This novel piezoelectric element is suitable for applications in piezoelectric devices such as ultrasonic motors, piezoelectric transformers, and ultrasonic transducers. It possesses high piezoelectric performance. 33 It also has a high mechanical quality factor, and its performance is significantly improved compared to the commonly used P-42, making it suitable for micro liquid cooling systems and microfluidic control in medical devices.

[0057] The above description is merely a description of preferred embodiments of the present invention and is not intended to limit the scope of the present invention in any way. Any changes or modifications made by those skilled in the art based on the above disclosure shall fall within the protection scope of the claims.

Claims

1. A lead-manganese antimonate-lead-indium niobate-lead zirconium titanate piezoelectric ceramic material, characterized by, The chemical general formula of the material composition is: 0.05 Pb(Mn 1 / 3 Sb 2 / 3 )]O3-0.92 Pb(Zr x Ti (1-x) ]O3-0.03 Pb(In 1 / 3 Nb 2 / 3 )]O3 + y wt% CuO + z wt% Fe2O3; wherein x = 0.5 to 0.6, y = 0.05 to 2, z = 0.05 to 3.

2. A lead-manganese-scheelite-lead-indium-lead-niobate-lead-zirconium-titanate piezoelectric ceramic material according to claim 1, characterized in that The x=0.53~0.55, y=0.25~1.5, z=0.

5.

3. A lead-manganese-scheelite-lead-indium-lead-niobate-lead-zirconium-titanate piezoelectric ceramic material according to claim 1, characterized in that The raw materials for preparing the piezoelectric ceramic material include Pb3O4, TiO2, ZrO2, MnO2, Nb2O5, In2O3, Sb2O3, CuO and Fe2O3.

4. A method for producing a lead manganonate-lead indium niobate-lead zirconium titanate piezoelectric ceramic material, for producing a lead manganonate-lead indium niobate-lead zirconium titanate piezoelectric ceramic material as claimed in any one of claims 1 to 3, characterized by, Comprise: Step S1: batching and mixing; the raw materials are weighed according to the stoichiometric ratio of the general formula, mixed and ball milled by a mixer, and the initial mixing time is 4h~12h; Step S2: pre-sintering; the powder obtained in step S1 is mixed with a small amount of deionized water and dry-pressed into a block, which is then placed in a crucible and pre-sintered in a muffle furnace to obtain a pre-sintered powder, and the pre-sintered powder is coarsely crushed; Step S3: secondary ball milling and granulation; the coarsely crushed powder obtained in step S2 is subjected to secondary ball milling for 24h by a ball mill, dried, and granulated by adding 7wt%~10wt% polyvinyl alcohol solution, and sieved, Step S4: forming; the sieved powder obtained in step S3 is tablet-pressed by a tablet press to prepare ceramic green bodies of specific shapes; Step S5: glue removal; the ceramic green body obtained in step S4 is placed in a muffle furnace for glue removal, and a ceramic green body after glue removal is obtained, wherein the glue removal temperature is 550℃, and the glue removal holding time is 2h; Step S6: sintering; the ceramic green body after glue removal obtained in step S5 is placed in a muffle furnace, covered with zirconium dioxide powder for buried sintering, and then naturally cooled to room temperature to obtain a ceramic sheet.

5. The preparation method of the lead manganese antimonate-lead indium niobate-lead zirconate titanate piezoelectric ceramic material as described in claim 4, characterized in that, In the step S2, the pre-sintering temperature is 800℃~850℃, the pre-sintering holding time is 2h, and the pre-sintering temperature rising speed is 3℃ / min~6℃ / min.

6. The preparation method of the lead manganese antimonate-lead indium niobate-lead zirconate titanate piezoelectric ceramic material as described in claim 5, characterized in that, The pre-sintering temperature is 820℃.

7. The preparation method of the lead manganese antimonate-lead indium niobate-lead zirconate titanate piezoelectric ceramic material as described in claim 4, characterized in that, In the step S6, the sintering temperature rising and falling parameters include: rising to 1000℃~1100℃ at a temperature rising speed of 3℃ / min~5℃ / min, holding for 1h, then rising to 1100℃~1280℃ at a temperature rising speed of 2℃ / min~3℃ / min, holding for 2h~3h, then falling to 800℃ at a temperature falling speed of 3℃ / min~10℃ / min, and then naturally cooling to room temperature.

8. The preparation method of the lead manganese antimonate-lead indium niobate-lead zirconate titanate piezoelectric ceramic material as described in claim 4, characterized in that, After the step S6, it further comprises: Step S7: polishing; the ceramic sheet obtained in step S6 is polished, ultrasonically cleaned, and then dried; Step S8: silver electrode sintering; the ceramic sheet dried in step S7 is brushed with silver electrodes on the surface requiring polarization, and then placed in a muffle furnace for silver sintering to obtain a silver-coated ceramic sheet; Step S9: polarization; the ceramic sheet obtained in step S8 is polarized, and the polarization process is that the electric field intensity is 3kv / mm~4kv / mm, the polarization temperature is 120℃, and the polarization time is 10min~30min.

9. The method of claim 8, wherein the manganese-sbafinate-lead-indium- niobate-lead-zirconium-titanate piezoelectric ceramic material is prepared by the steps of: mixing the ingredients of the manganese-sbafinate-lead-indium- niobate-lead-zirconium-titanate piezoelectric ceramic material; forming the mixture into a green body; and sintering the green body. In the step S8, the silver sintering temperature rising speed is 3℃ / min~10℃ / min, and the temperature rising range is 750℃~850℃, and the temperature holding time is 20min~40min.