Bismuth yttrium acid-lead zirconate titanate piezoelectric ceramic material and preparation method thereof

Abstract

The invention belongs to the technical field of piezoelectric ceramics, and particularly relates to a bismuth yttrium acid-lead zirconate titanate piezoelectric ceramic material and a preparation method thereof. Comprising the following chemical general formula: xBiYO3-(1-x) Pb0. 99Nd0.01 (ZryTi1-y) O3 + zwt% CuO, wherein x ranges from 0.001 to 0.05, y ranges from 0.5 to 56, and z ranges from 0 to 2. The piezoelectric ceramic material is prepared from the following raw materials: Pb3O4, TiO2, ZrO2, Y2O3, Bi2O3, Nd2O3 and CuO. The multilayer piezoelectric ceramic has the advantages of higher piezoelectric property, relatively lower dielectric constant and lower sintering temperature, the production cost of the piezoelectric ceramic is reduced, and the multilayer piezoelectric ceramic can be applied to a multilayer piezoelectric ceramic preparation process. The piezoelectric loudspeaker can be applied to ultra-thin electronic equipment due to the performance characteristics of the piezoelectric loudspeaker.

Description

Technical Field

[0001] This invention belongs to the field of piezoelectric ceramic technology, and specifically relates to a bismuth yttrium-lead zirconate titanate piezoelectric ceramic material and its preparation method. Background Technology

[0002] The current trend in mobile electronic devices is towards ultra-thin and ultra-small sizes. The conical shape of traditional speakers is difficult to integrate into ultra-thin and small devices, necessitating the use of piezoelectric speakers instead. However, traditional piezoelectric materials such as the P-4 series are not suitable for manufacturing piezoelectric speakers. Therefore, it is necessary to develop piezoelectric ceramics with high piezoelectric performance and low dielectric constant.

[0003] In view of the above requirements, a more in-depth study is needed on the composition, structure and properties of bismuth yttrium oxide-lead zirconate titanate materials, 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 bismuth yttrium-lead zirconate titanate piezoelectric ceramic material and its preparation method. This invention solves the performance limitations of conventional P-4 piezoelectric materials and meets the needs of the piezoelectric loudspeaker field for piezoelectric materials.

[0005] To address the aforementioned technical problems, this invention provides a bismuth yttrium-lead zirconate titanate piezoelectric ceramic material, the general chemical formula of which is xBiYO3-(1-x)Pb. 0.99 Nd 0.01 (Zr y Ti 1-y )O3+zwt%CuO; where x=0.001~0.05, y=0.5~56, z=0~2.

[0006] Preferably, x = 0.01 to 0.03, y = 0.53 to 0.55, and z = 0.5.

[0007] Preferably, the raw materials for preparing the piezoelectric ceramic material include Pb3O4, TiO2, ZrO2, Y2O3, Bi2O3, Nd2O3 and CuO.

[0008] This invention also provides a method for preparing a bismuth yttrium-lead zirconate titanate piezoelectric ceramic material, comprising:

[0009] Step S1: Ingredient preparation and precursor preparation; Weigh the raw materials according to the stoichiometric ratio of the general formula. First, prepare the BiYO3 precursor by ball milling Y2O3 and Bi2O3 together for 10 hours. Then, dry and pre-calcine at 850°C. Next, ball mill the pre-calcine powder with Pb3O4, TiO2, ZrO2, CuO and Nd2O3 a second time using deionized water as the mixing medium. After mixing, dry to obtain the powder.

[0010] Step S2: Pre-calcination; The powder obtained in step S1 is mixed with a small amount of deionized water and pressed into blocks by a press. The blocks are placed in a crucible and then pre-calcined in a muffle furnace to obtain pre-calcined powder. After pre-calcination, the powder is coarsely crushed.

[0011] Step S3: Secondary ball milling; The powder coarsely crushed in step S2 is subjected to secondary ball milling and drying, then 7wt%~12wt% polyvinyl alcohol solution is added for uniform grinding and sieve; the secondary ball milling time is 24 hours.

[0012] Step S4: Forming; The powder sieved in step S3 is pressed into tablets using a tablet press to form a ceramic blank;

[0013] 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.

[0014] 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.

[0015] Preferably, in step S2, the pre-firing heating rate is 3℃ / min to 5℃ / min, the pre-firing temperature is 850℃, and the pre-firing holding time is 2h.

[0016] Preferably, in step S3, the amount of polyvinyl alcohol solution added is 8 wt% to 10 wt%.

[0017] Preferably, in step S6, the sintering temperature rise and fall parameters include: rising to 900℃ to 1000℃ at a rising rate of 4℃ / min to 5℃ / min, holding at that temperature for 2 hours, and then naturally cooling to room temperature.

[0018] Preferably, after step S6, the method further includes:

[0019] Step S7: Polishing; Polish the ceramic sheet obtained in step S6, and then clean and dry it;

[0020] 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.

[0021] Step S9: Polarization; The ceramic sheet obtained in step S8 is polarized. The polarization process is to use an electric field strength of 4kV / mm to 6kV / mm and a polarization time of 10min to 30min.

[0022] Preferably, in step S8, the silver is heated to 650-750°C at a rate of 3°C / min to 10°C / min, and held at this temperature for 20-40 minutes.

[0023] Compared with the prior art, the present invention has the following beneficial effects:

[0024] This invention designs an xBiYO3-(1-x)Pb 0.99 Nd 0.01 (Zr y Ti 1-y O3+zwt%CuO piezoelectric ceramic, which has high piezoelectricity. 33 While achieving a dielectric constant of 570 pC / N, it also possesses a relatively low dielectric constant of 800, making it more suitable for piezoelectric loudspeakers compared to conventional piezoelectric ceramics. The xBiYO3-(1-x)Pb of this invention... 0.99 Nd 0.01 (Zr y Ti 1-y O3+zwt%CuO piezoelectric ceramics have a lower sintering temperature, which can match the process of multilayer piezoelectric ceramics. Detailed Implementation

[0025] 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.

[0026] Example 1

[0027] A high-power lead manganese niobate-lead zirconate titanate piezoelectric ceramic material according to an embodiment of the present invention has the general chemical formula xBiYO3-(1-x)Pb 0.99 Nd 0.01 (Zr 0.535 Ti 0.465 O3 + 0.5wt% CuO, where x = 0.01.

[0028] Specifically, the preparation methods include the following:

[0029] S1: Ingredient preparation and precursor preparation. First, BiYO3 precursor is prepared by weighing Y2O3 and Bi2O3 in proportion and mixing them. The initial ball milling time is 10 hours, followed by drying and pre-calcination at 850℃. Then, the pre-calcined powder is mixed with Pb3O4, TiO2, ZrO2, CuO, and Nd2O3 using a ball mill with deionized water as the mixing medium. After mixing, the powder is dried.

[0030] S2: Mix the powder from S1 with a small amount of water, press it into blocks using a press, place it in a crucible, and then pre-calcine the powder in a muffle furnace. The heating rate is 3℃ / min~5℃ / min, the pre-calcine temperature is 850℃, and the pre-calcine holding time is 2 hours to obtain pre-calcined powder. After pre-calcination, the powder is coarsely crushed.

[0031] S3: The powder obtained in S2 is subjected to secondary ball milling and drying, and then polyethylene solution is added and ground evenly. The amount of polyvinyl alcohol added is 7wt% to 12wt%. The secondary ball milling time is 24 hours, and then the powder is sieved.

[0032] S4: The powder obtained in step S3 is pressed into tablets using a tablet press to form a ceramic blank.

[0033] S5: Place the preform obtained in S4 into a muffle furnace for debinding to obtain a debinded preform. The debinding temperature is 550℃ and the debinding holding time is 2 hours.

[0034] S6: Place the debinding preform obtained in S5 into a muffle furnace, cover the preform with zirconium dioxide powder and fire it to obtain ceramic sheets. The sintering temperature rise and fall regime is as follows: heat up to 900-1000℃ at a rise rate of 4℃ / min to 5℃ / min, hold for 2 hours and then cool naturally to room temperature.

[0035] S7: Polish and clean the ceramic obtained in S6.

[0036] S8: Brush a silver electrode onto the ceramic surface that needs to be polarized using S7, then place it in a muffle furnace to burn silver. Increase the temperature at a rate of 3℃ / min to 10℃ / min to 650 to 750℃, and hold at this temperature for 20 to 40 minutes to obtain a silver-coated ceramic sheet.

[0037] S9: The ceramic obtained in S8 is polarized. The polarization process involves an electric field strength of 4kV / mm to 6kV / mm and a polarization time of 10 to 30 minutes. After polarization, it is cleaned. After cleaning, it is placed for 24 hours before testing.

[0038] Example 2

[0039] The only difference between this embodiment and Embodiment 1 is that its chemical formula is xBiYO3-(1-x)Pb 0.99 Nd 0.01 (Zr 0.535 Ti 0.465 O3 + 0.5wt% CuO, where x = 0.02.

[0040] Example 3

[0041] The only difference between this embodiment and Embodiment 1 is that its chemical formula is xBiYO3-(1-x)Pb 0.99 Nd 0.01 (Zr 0.535 Ti 0.465 O3 + 0.5wt% CuO, where x = 0.03.

[0042] Example 4

[0043] The only difference between this embodiment and Embodiment 1 is that its chemical formula is 0.01BiYO3-0.99Pb. 0.99 Nd 0.01 (Zr y Ti 1-y O3 + 0.5wt% CuO, where y = 0.53.

[0044] Example 5

[0045] The only difference between this embodiment and Embodiment 1 is that its chemical formula is 0.01BiYO3-0.99Pb. 0.99 Nd 0.01 (Zr y Ti 1-y O3 + 0.5wt% CuO, where y = 0.54.

[0046] Example 6

[0047] The only difference between this embodiment and Embodiment 1 is that its chemical formula is 0.01BiYO3-0.99Pb. 0.99 Nd 0.01 (Zr y Ti 1-y O3 + 0.5wt% CuO, where y = 0.55.

[0048] The electrical performance test results of Examples 1 to 3 are shown in Table 1 below.

[0049] Table 1. Data on piezoelectric and dielectric properties.

[0050] Example Components <![CDATA[d 33 (pC / N)]]> kp <![CDATA[ε r ]]> Example 1 x＝0.01 535 0.63 900 Example 2 x＝0.02 390 0.60 835 Example 3 x＝0.03 278 0.56 854

[0051] The electrical performance test results of Examples 4 to 6 are shown in Table 2 below.

[0052] Table 2. Data on piezoelectric and dielectric properties.

[0053] Example Components <![CDATA[d 33 (pC / N)]]> kp <![CDATA[ε r ]]> Example 4 y＝0.53 470 0.61 882 Example 5 y＝0.54 556 0.63 925 Example 6 y＝0.55 358 0.59 850

[0054] In summary, this invention designs a bismuth yttrium acid-lead zirconate titanate xBiYO3-(1-x)Pb 0.99 Nd 0.01 (Zr y Ti 1-y This paper presents a piezoelectric ceramic material (O3+zwt%CuO) and its preparation method. The material exhibits high piezoelectric properties and a relatively low dielectric constant, along with a low sintering temperature, reducing the production cost of piezoelectric ceramics and making it suitable for multilayer piezoelectric ceramic fabrication processes. Its performance characteristics enable its application in piezoelectric speakers for ultra-thin electronic devices.

[0055] 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 bismuth yttrium-lead zirconate titanate piezoelectric ceramic material, characterized in that, Its general chemical formula is represented as xBiYO3-(1-x)Pb 0.99 Nd 0.01 (Zr y Ti 1-y )O3+zwt%CuO; where x=0.001~0.05, y=0.5~56, z=0~2.

2. The bismuth yttrium oxide-lead zirconate titanate piezoelectric ceramic material as described in claim 1, characterized in that, The values ​​are x = 0.01 to 0.03, y = 0.53 to 0.55, and z = 0.

5.

3. The bismuth yttrium oxide-lead zirconate titanate piezoelectric ceramic material as described in claim 1, characterized in that, The raw materials for preparing the piezoelectric ceramic material include Pb3O4, TiO2, ZrO2, Y2O3, Bi2O3, Nd2O3 and CuO.

4. A method for preparing a bismuth yttrium-lead zirconate titanate piezoelectric ceramic material, characterized in that, include: Step S1: Ingredient preparation and precursor preparation; Weigh the raw materials according to the stoichiometric ratio of the general formula. First, prepare the BiYO3 precursor by ball milling Y2O3 and Bi2O3 together for 10 hours. Then, dry and pre-calcine at 850°C. Next, ball mill the pre-calcine powder with Pb3O4, TiO2, ZrO2, CuO and Nd2O3 a second time using deionized water as the mixing medium. After mixing, dry to obtain the powder. Step S2: Pre-calcination; The powder obtained in step S1 is mixed with a small amount of deionized water and pressed into blocks by a press. The blocks are placed in a crucible and then pre-calcined in a muffle furnace to obtain pre-calcined powder. After pre-calcination, the powder is coarsely crushed. Step S3: Secondary ball milling; The powder coarsely crushed in step S2 is subjected to secondary ball milling and drying, then 7wt%~12wt% polyvinyl alcohol solution is added for uniform grinding and sieve; the secondary ball milling time is 24 hours. Step S4: Forming; The powder sieved in step S3 is pressed into tablets using a tablet press to form a ceramic blank; 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. 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.

5. The method for preparing a bismuth yttrium-lead zirconate titanate piezoelectric ceramic material as described in claim 4, characterized in that, In step S2, the pre-firing heating rate is 3℃ / min to 5℃ / min, the pre-firing temperature is 850℃, and the pre-firing holding time is 2h.

6. The method for preparing a bismuth yttrium-lead zirconate titanate piezoelectric ceramic material as described in claim 4, characterized in that, In step S3, the amount of polyvinyl alcohol solution added is 8 wt% to 10 wt%.

7. The method for preparing a bismuth yttrium-lead zirconate titanate piezoelectric ceramic material as described in claim 4, characterized in that, In step S6, the sintering temperature rise and fall parameters include: rising to 900℃ to 1000℃ at a rising rate of 4℃ / min to 5℃ / min, holding at that temperature for 2 hours, and then naturally cooling to room temperature.

8. The method for preparing a bismuth yttrium-lead zirconate titanate piezoelectric ceramic material as described in claim 4, characterized in that, Following step S6, the method further includes: Step S7: Polishing; Polish the ceramic sheet obtained in step S6, and then clean and dry it; 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. Step S9: Polarization; The ceramic sheet obtained in step S8 is polarized. The polarization process is to use an electric field strength of 4kV / mm to 6kV / mm and a polarization time of 10min to 30min.

9. The method for preparing a bismuth yttrium-lead zirconate titanate piezoelectric ceramic material as described in claim 8, characterized in that, In step S8, the silver is heated to 650-750°C at a rate of 3°C / min to 10°C / min, and held at this temperature for 20-40 minutes.