Lead antimonate niobate-lead manganese 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 antimonate niobate-lead manganese niobate-lead zirconate titanate piezoelectric ceramic material and a method. Comprising a chemical general formula of xPb (Sb1 / 3Nb2 / 3) O3 <-0.04 > Pb (Mn1 / 3Nb2 / 3) O3 <-(0.96-x) Pb < 0.98 > Sr < 0.02 > (Zr < 0.5 > Ti < 0.5 >) O3 < + y wt% Fe < 2 > O < 3 >, wherein x is equal to 0.01 to 0.08, and y is equal to 0.01 to 2. The piezoelectric ceramic material is prepared from the following raw materials: Pb3O4, TiO2, ZrO2, Nb2O5, Sb2O3, MnO2 and SrCO3. The piezoelectric ceramic has a high piezoelectric coefficient and a high electromechanical coupling coefficient at the same time, compared with traditional P-8 series piezoelectric ceramics, the energy conversion rate can be improved, and the piezoelectric ceramic has low dielectric loss and high mechanical quality factor together with P-8 and has low loss in the energy conversion process.

Description

Technical Field

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

[0002] Piezoelectric ceramics enable the conversion between electrical and mechanical energy and are widely used in piezoelectric sensors, transformers, transducers, and other devices. Currently, the application of piezoelectric transducers has expanded to mobile devices, medical devices, energy harvesting, and other fields. Piezoelectric devices possess advantages such as simple structure, high efficiency, compact design, and light weight. Some piezoelectric devices utilize both the inverse piezoelectric effect and the piezoelectric effect; therefore, it is necessary to develop devices that simultaneously possess high electromechanical coefficients and high electromechanical coupling coefficients to improve energy conversion efficiency, as well as low dielectric loss and high mechanical quality factor to reduce losses during energy conversion.

[0003] In view of the above requirements, a more in-depth study is needed on the composition, structure and properties of lead antimony niobate-lead manganese niobate-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 lead antimony niobate-lead manganese niobate-lead zirconate titanate piezoelectric ceramic material and method. This invention solves the problem of limited performance of conventional P-8 piezoelectric materials and meets the needs of high performance and high mechanical quality factor scenarios. It has a higher mechanical quality factor, higher piezoelectric performance, and lower dielectric loss, and can be applied to power piezoelectric transducers.

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

[0006] xPb(Sb 1 / 3 Nb 2 / 3 O3-0.04Pb(Mn) 1 / 3 Nb 2 / 3 )O3-(0.96-x)Pb 0.98 Sr 0.02 (Zr 0.5 Ti 0.5 )O3+ywt%Fe2O3; where x=0.01~0.08, y=0.01~2.

[0007] Preferably, x = 0.01 to 0.05 and y = 0.2 to 0.75.

[0008] Preferably, the raw materials for preparing the piezoelectric ceramic material include Pb3O4, TiO2, ZrO2, Nb2O5, Sb2O3, MnO2 and SrCO3.

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

[0010] Step S1: Ingredient mixing; Weigh the raw materials according to the general stoichiometric ratio, select a ball mill for initial mixing and ball milling for 12 hours, and then dry them;

[0011] Step S2: Pre-calcination; The powder dried 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. The pre-calcined powder 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: Forming; The powder sieved in step S3 is pressed into tablets using a tablet press to form a ceramic blank;

[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 10℃ / min, the pre-firing temperature is 800℃ to 850℃, and the pre-firing holding time is 2h.

[0017] Preferably, the preheating temperature is 820°C.

[0018] Preferably, in step S6, the sintering temperature rise and fall parameters include: rising to 1000°C at a rising rate of 3°C / min, holding for 1 hour, then rising to 1160°C at a rising rate of 2°C / min, holding for 3 hours, and after holding, cooling down to 800°C at a cooling rate of 3°C / min to 10°C / 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 4kv / mm to 5kv / mm, the polarization temperature is 130℃, and the polarization time is 10min to 30min.

[0023] Preferably, in step S8, the silver is heated to 700°C to 800°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 prepares a lead antimony niobate-lead manganese niobate-lead zirconate titanate piezoelectric ceramic material with the chemical formula xPb(Sb) 1 / 3Nb 2 / 3 O3-0.04Pb(Mn) 1 / 3 Nb 2 / 3 )O3-(0.96-x)Pb 0.98 Sr 0.02 (Zr 0.5 Ti 0.5 The material, consisting of O3 + 0.25wt% Fe2O3 (x = 0.01–0.08, y = 0.01–2), possesses both good piezoelectric properties and a high mechanical quality factor. This piezoelectric ceramic exhibits both a high piezoelectric coefficient and a high electromechanical coupling coefficient. Compared to traditional P-8 series piezoelectric ceramics, it can improve energy conversion efficiency and, like P-8, possesses low dielectric loss and a high mechanical quality factor, resulting in lower losses during energy conversion. 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 antimony niobate-lead manganese niobate-lead zirconate titanate piezoelectric ceramic material, the chemical formula of which is:

[0029] xPb(Sb 1 / 3 Nb 2 / 3 O3-0.04Pb(Mn) 1 / 3 Nb 2 / 3 )O3-(0.96-x)Pb 0.98 Sr 0.02 (Zr0.5 Ti 0.5 )O3+ywt%Fe2O3, where x=0.01, y=0.2.

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

[0031] S1: Weigh the ingredients according to the general chemical formula, then ball mill and dry them. The ball milling medium is deionized water. After ball milling for 12 hours, dry them.

[0032] S2: The dried powder is pressed into blocks using a dry press, placed in a crucible, and pre-fired in a muffle furnace. The pre-firing heating rate is 3℃ / min, the pre-firing temperature is 800℃, and the pre-firing holding time is 2h. After cooling, the powder is coarsely crushed using a pulverizer to obtain pre-fired powder.

[0033] S3: Secondary ball milling. The powder obtained in S2 is subjected to secondary ball milling for 24 hours. After drying, it is added to a polyethylene solution and stirred evenly with a mixer. Then, it is granulated using a granulator.

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

[0035] S5: Debonding. The preform obtained in S4 is placed in a muffle furnace for debonding at a temperature of 550℃ for 2 hours. The debonded preform is then obtained.

[0036] S6: Sintering. The debinding body obtained in S5 is placed in a muffle furnace and covered with zirconium dioxide powder for sintering. The sintering temperature regulation is as follows: the temperature is increased to 1000℃ at a rate of 3℃ / min and held for 1 hour. Then, the temperature is increased to 1160℃ at a rate of 2℃ / min and held for 3 hours. After the holding period, the temperature is reduced to 800℃ at a rate of 4℃ / min and then naturally cooled to room temperature to obtain ceramic sheets.

[0037] S7: Machining. The ceramic obtained in S6 is machined to form the designed shape. After machining, it is cleaned with an ultrasonic cleaner.

[0038] S8: Silver electrode firing. Apply the silver electrode to the ceramic surface that needs to be polarized using S7, then place it in a muffle furnace to fire the silver. The temperature is increased to 800℃ at a rate of 3℃ / min, and held at this temperature for 30min. Then, it is cooled with the furnace.

[0039] S9: Polarization test. The ceramic obtained in S8 was polarized with silicone oil at a polarization voltage of 4kV / mm and a polarization temperature of 130℃ for 20 minutes. After polarization, it was cleaned with a cleaning agent. The ceramic was tested after being left to stand for 24 hours.

[0040] Example 2

[0041] The only difference between this embodiment and Embodiment 1 is that its chemical formula is xPb(Sb) 1 / 3 Nb 2 / 3 O3-0.04Pb(Mn) 1 / 3 Nb 2 / 3 )O3-(0.96-x)Pb 0.98 Sr 0.02 (Zr 0.5 Ti 0.5 )O3+ywt%Fe2O3, where x=0.03, y=0.2.

[0042] Example 3

[0043] The only difference between this embodiment and Embodiment 1 is that its chemical formula is xPb(Sb) 1 / 3 Nb 2 / 3 O3-0.04Pb(Mn) 1 / 3 Nb 2 / 3 )O3-(0.96-x)Pb 0.98 Sr 0.02 (Zr 0.5 Ti 0.5 )O3+ywt%Fe2O3, where x=0.05, y=0.2.

[0044] Example 4

[0045] The only difference between this embodiment and Embodiment 1 is that its chemical formula is xPb(Sb) 1 / 3 Nb 2 / 3 O3-0.04Pb(Mn) 1 / 3 Nb 2 / 3 )O3-(0.96-x)Pb 0.98 Sr 0.02 (Zr 0.5 Ti 0.5 )O3+ywt%Fe2O3, where x=0.03, y=0.25.

[0046] Example 5

[0047] The only difference between this embodiment and Embodiment 1 is that its chemical formula is xPb(Sb) 1 / 3 Nb 2 / 3 O3-0.04Pb(Mn) 1 / 3 Nb 2 / 3 )O3-(0.96-x)Pb 0.98 Sr 0.02 (Zr 0.5 Ti 0.5 )O3+ywt%Fe2O3, where x=0.03, y=0.5.

[0048] Example 6

[0049] The only difference between this embodiment and Embodiment 1 is that its chemical formula is xPb(Sb) 1 / 3 Nb 2 / 3 O3-0.04Pb(Mn) 1 / 3 Nb 2 / 3 )O3-(0.96-x)Pb 0.98 Sr 0.02 (Zr 0.5 Ti 0.5 )O3+ywt%Fe2O3, where x=0.03, y=0.75.

[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]

[0053]

[0054] The electrical performance test results of Examples 4 to 6 above are shown in Table 2 below.

[0055] Table 2. Data on piezoelectric and dielectric properties.

[0056] Example Components <![CDATA[d 33 (pC / N)]]> tanδ kp <![CDATA[Q m ]]> Example 4 y＝0.25 330 0.40％ 0.58 1465 Example 5 y＝0.5 368 0.39％ 0.61 1360 Example 6 y＝0.75 326 0.35％ 0.57 1224

[0057] In summary, this invention designs a lead antimony niobate-lead manganese niobate-lead zirconate titanate piezoelectric ceramic material with the molecular formula xPb(Sb) 1 / 3 Nb 2 / 3 O3-0.04Pb(Mn) 1 / 3 Nb 2 / 3 )O3-(0.96-x)Pb 0.98 Sr 0.02 (Zr 0.5 Ti 0.5 The piezoelectric ceramic )O3+ywt%Fe2O3 (x=0.01~0.08,y=0.01~2) has both high voltage coefficient and high electromechanical coupling coefficient. Compared with the traditional P-8 series piezoelectric ceramics, it can improve the energy conversion efficiency. In addition, together with P-8, it has low dielectric loss and high mechanical quality factor, and has low loss in the energy conversion process.

[0058] 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 antimony niobate-lead manganese niobate-lead zirconate titanate piezoelectric ceramic material, characterized in that, The general chemical formula for its material composition is: xPb(Sb 1 / 3 Nb 2 / 3 )O3-0.04Pb(Mn 1 / 3 Nb 2 / 3 )O3-(0.96-x)Pb 0.98 Sr 0.02 (Zr 0.5 Ti 0.5 )O3 + y wt% Fe2O3; where x = 0.01 to 0.08 and y = 0.01 to 2.

2. The lead antimony niobate-lead manganese niobate-lead zirconate titanate piezoelectric ceramic material and method as described in claim 1, characterized in that, The values ​​are x = 0.01 to 0.05 and y = 0.2 to 0.

75.

3. The lead antimony niobate-lead manganese niobate-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, Nb2O5, Sb2O3, MnO2 and SrCO3.

4. A method for preparing a lead antimony niobate-lead manganese niobate-lead zirconate titanate piezoelectric ceramic material, characterized in that, include: Step S1: Ingredient mixing; Weigh the raw materials according to the general stoichiometric ratio, select a ball mill for initial mixing and ball milling for 12 hours, and then dry them; Step S2: Pre-calcination; The powder dried 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. The pre-calcined powder is then coarsely crushed. 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. 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 preparation method of the lead antimony niobate-lead manganese niobate-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 10℃ / min, the pre-firing temperature is 800℃ to 850℃, and the pre-firing holding time is 2h.

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

7. The preparation method of the lead antimony niobate-lead manganese niobate-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 1000°C at a rising rate of 3°C / min, holding for 1 hour, then rising to 1160°C at a rising rate of 2°C / min, holding for 3 hours, and after holding, cooling down to 800°C at a cooling rate of 3°C / min to 10°C / min, and then naturally cooling to room temperature.

8. The preparation method of the lead antimony niobate-lead manganese niobate-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 perform ultrasonic cleaning and drying. 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 as follows: the electric field strength is 4kv / mm to 5kv / mm, the polarization temperature is 130℃, and the polarization time is 10min to 30min.

9. The preparation method of the lead antimony niobate-lead manganese niobate-lead zirconate titanate piezoelectric ceramic material as described in claim 8, characterized in that, In step S8, the silver is heated to 700°C to 800°C at a rate of 3°C / min to 10°C / min, and held at this temperature for 20 min to 40 min.

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