A wide-temperature-range manganese-yttrium co-doped PMS-PZT piezoelectric ceramic material and a preparation method thereof

Abstract

A kind of wide temperature range manganese yttrium co-doped PMS-PZT piezoelectric ceramic material and its preparation method, wide temperature range manganese yttrium co-doped PMS-PZT piezoelectric ceramic material is doped with 0.25~0.35wt% Mn3O4 / Y2O3 in PMS-PZT ceramic, wherein the ratio of Mn3O4 / Y2O3 is (3~0): (0~3);The manganese yttrium co-doped PMS-PZT ceramic of the application has enhanced piezoelectric performance and optimized dielectric characteristics, and also has good thermal stability and fatigue resistance, can effectively resist performance decay in wide temperature range cycle and long time high electric field driving process, and shows excellent service life;Manganese yttrium co-doped PMS-PZT ceramic material uses conventional oxide raw material and solid phase sintering method, with the advantages of simple preparation process, controllable cost, high repeatability, suitable for large-scale industrial production and application.

Description

Technical Field

[0001] This invention belongs to the field of piezoelectric ceramic material preparation technology, and relates to a method for preparing wide-temperature-range manganese yttrium co-doped PMS-PZT piezoelectric ceramic materials. Background Technology

[0002] Piezoelectric ceramics are core functional materials for converting mechanical energy into electrical energy, and their performance directly determines the efficiency and reliability of key components such as sensors, transducers, and actuators. Among numerous piezoelectric material systems, PMS-PZT(Pb(Mg)) stands out. 1 / 3 Sb 2 / 3 PbO3-PbZrO3-PbTiO3 ceramics are considered ideal candidates for high-power, wide-temperature-range applications due to their high Curie temperature and tunable phase structure. However, intrinsic PMS-PZT ceramics suffer from domain wall instability, high dielectric loss, and insufficient fatigue resistance under high driving fields, which limits their long-term stable application in harsh environments.

[0003] Elemental doping is an effective way to optimize overall performance. Manganese (Mn) doping, as a typical "acceptor doping," can effectively introduce oxygen vacancies, pin domain walls, reduce dielectric loss, and improve the mechanical quality factor; while yttrium (Y) doping, as a "donor doping," can replace Pb at A sites. 2+ This leads to lattice distortion, enhances spontaneous polarization, and improves the temperature stability of the material. However, existing technologies mostly focus on single-element doping, making it difficult to simultaneously achieve high voltage activity and high stability. Especially for the manganese-yttrium co-doping strategy, the two elements occupy B-sites and A-sites in the PMS-PZT lattice, respectively, and the synergistic mechanism between them remains unclear—for example, Y... 3+ How does the introduction of Mn affect 2+ / Mn 3+ The valence state and occupancy of oxygen vacancies, their synergistic regulation of oxygen vacancy formation and distribution, and how they ultimately optimize the domain structure and macroscopic electrical properties of materials all require further investigation.

[0004] Therefore, it is necessary to develop a method for preparing PMS-PZT ceramics that can precisely control the ratio and distribution of manganese and yttrium doping, so as to provide a new solution for developing PMS-PZT piezoelectric ceramic materials with excellent comprehensive performance and high reliability, and promote their application in high-performance piezoelectric devices. Summary of the Invention

[0005] The first technical problem to be solved by the present invention is to provide a wide-temperature-range manganese-yttrium co-doped PMS-PZT piezoelectric ceramic material. By co-doping manganese and yttrium and reasonably controlling the doping ratio of manganese and yttrium, the material has good long-term temperature thermal stability and fatigue resistance, and can effectively resist the performance degradation during wide-temperature-range cycling and long-term high electric field driving process, thus exhibiting excellent service life.

[0006] The second technical problem to be solved by the present invention is to provide a simple and repeatable method for preparing wide-temperature-range manganese yttrium co-doped PMS-PZT piezoelectric ceramic materials. The prepared manganese yttrium co-doped PMS-PZT ceramics have good thermal stability and fatigue resistance, and can effectively resist performance degradation during wide-temperature-range cycling and long-term high-electric-field driving processes, exhibiting excellent service life.

[0007] The technical solution adopted by the present invention to solve the first technical problem mentioned above is: a wide-temperature-range manganese yttrium co-doped PMS-PZT piezoelectric ceramic material, characterized in that: the wide-temperature-range manganese yttrium co-doped PMS-PZT piezoelectric ceramic material is PMS-PZT ceramic doped with 0.25~0.35wt% Mn3O4 / Y2O3, wherein the weight ratio of Mn3O4 / Y2O3 is (3~0):(0~3).

[0008] Preferably, the PMS-PZT ceramic composition is Pb(Mn) 1 / 3 Sb 2 / 3 ) 0.05 Zr 0.475 Ti 0.475 The doping amount of O3, Mn3O4 / Y2O3 is 0.3wt%, and the ratio of Mn3O4 / Y2O3 is 1:1.

[0009] The technical solution adopted by the present invention to solve the second technical problem mentioned above is: a method for preparing the above-mentioned wide-temperature-range manganese yttrium co-doped PMS-PZT piezoelectric ceramic material, characterized by comprising the following steps:

[0010] 1) Weigh the Pb3O4, TiO2, ZrO2, Mn3O4, Sb3O4, and Y2O3 powders according to a certain stoichiometric ratio, and then place them in a planetary ball mill to ball mill until they are mixed evenly.

[0011] 2) After the ball milling slurry is dried, sieved, and pre-pressed, it is placed in an alumina crucible and heated to the reaction temperature of 400-1200℃ at a rate of 2-10℃ / min. The temperature is maintained for 1-5 hours to pre-synthesize ceramic powder. Then, it is crushed and further ball milled to obtain fine ceramic powder.

[0012] 3) After the ceramic powder is ball-milled and dried twice, it is sieved, an appropriate amount of polyvinyl alcohol binder is added, mixed evenly and granulated. After granulation, it is sieved through a certain sieve and placed in a mold to be pressed into a round ceramic green body with a certain diameter and thickness.

[0013] 4) The formed ceramic green body is heated to 500℃-800℃ at a rate of 1℃ / min-10℃ / min and held for 1h-5h to volatilize and remove the polyvinyl alcohol binder. The powder is then evenly spread and buried for firing. The temperature is then increased to 500℃-1500℃ at a rate of 1℃ / min-10℃ / min and held for 1h-10h for solid-state sintering to obtain the ceramic sample.

[0014] 5) Thin the sintered ceramic sample to less than 2 mm, apply silver paste to its upper and lower surfaces as electrodes, and then heat it at 500℃-1000℃ for 2-10 min to allow the silver electrodes to bond tightly with the ceramic surface, thus obtaining the final ceramic sample.

[0015] Preferably, the ball milling speed in step 1) is 300 r / min-600 r / min, and the ball milling time is 4-20 h.

[0016] Preferably, in step 2), the ball milling speed is 300 r / min-600 r / min, and the ball milling time is 4-20 h.

[0017] Furthermore, in step 3), the sieve particle size is 50μm-300μm; the mass fraction of the added polyvinyl alcohol binder is 1%-10%, and it is sieved through a 20-100 mesh sieve after granulation.

[0018] Furthermore, the granulated and sieved powder from step 3) is placed in a mold and pressed into a circular ceramic green body with a diameter of about 15-16 mm and a thickness of about 1.4-1.6 mm under a pressure of 90-110 MPa.

[0019] Furthermore, step 4) involves placing the ceramic green body after debinding into a crucible containing ceramic atmosphere powder of the corresponding components for firing.

[0020] Finally, the upper and lower surfaces of the ceramic sample in step 5) are coated with silver paste by screen printing.

[0021] Compared with the prior art, the advantages of the present invention are as follows:

[0022] (1) The composition of the manganese yttrium co-doped PMS-PZT ceramic of the present invention includes a perovskite phase matrix and manganese elements (Mn) occupying the B site. 2+ / Mn 3+ ) and yttrium (Y) occupying position A 3+The ceramic has a dense microstructure and uniform grain size. The introduction of yttrium can effectively refine the grains, while the synergistic effect of manganese and yttrium can precisely control the oxygen vacancy concentration. The doping ratio of manganese and yttrium can be controlled by optimizing the batching calculation and sintering process. The addition amount of Mn3O4 and Y2O3, sintering temperature and holding time can be adjusted and optimized, resulting in good process repeatability.

[0023] (2) The manganese-yttrium co-doped PMS-PZT ceramic of the present invention has enhanced piezoelectric properties and optimized dielectric properties. Yttrium doping helps to improve the spontaneous polarization intensity, while manganese doping can significantly reduce dielectric loss by pinning domain walls with oxygen vacancies. The synergistic effect of the two allows the ceramic to maintain a high piezoelectric coefficient (d 33 While possessing ≥ 300 pC / N, it also has a high mechanical quality factor (Q). m (≥ 800), thereby improving its stability and reliability under high voltage electric fields;

[0024] (3) The manganese yttrium co-doped PMS-PZT ceramic of the present invention has good thermal stability and fatigue resistance, and can effectively resist performance degradation during wide temperature range cycling and long-term high electric field driving process, showing excellent service life.

[0025] (4) The manganese yttrium co-doped PMS-PZT ceramic material of the present invention adopts conventional oxide raw materials and solid-state sintering method, which has the advantages of simple preparation process, controllable cost and high repeatability, and is suitable for large-scale industrial production and application. Attached Figure Description

[0026] Figure 1 This is a process flow diagram of the preparation process of manganese yttrium co-doped PMS-PZT ceramic material provided by the present invention;

[0027] Figure 2 XRD patterns of ceramic samples prepared for this example;

[0028] Figure 3 The images show a comparison of the SEM microstructures of ceramics with different manganese yttrium doping in the examples; the compositions are (a) Mn / Y = 3 / 0, (b) Mn / Y = 2 / 1, (c) Mn / Y = 1.5 / 1.5, (d) Mn / Y = 1 / 2, (e) Mn / Y = 0 / 3, and (f) shows the changes in grain size and density with composition.

[0029] Figure 4 The Curie temperature of the PMS-PZT ceramic sample in the example varies with the manganese yttrium doping ratio.

[0030] Figure 5The electrical performance parameters of the manganese yttrium co-doped PMS-PZT piezoelectric ceramic samples in the examples are shown below; the piezoelectric constant d of the manganese yttrium co-doped PMS-PZT is also shown below. 33 Electromechanical coupling coefficient k p Mechanical quality factor Q m Relative permittivity ε r Dielectric loss tanδ;

[0031] Figure 6 M in the example 0.15 Y 0.15 The piezoelectric constant d of the ceramic sample after polarization at 270℃ 33 Curve showing how it changes over time. Detailed Implementation

[0032] This application provides a method for preparing wide-temperature-range manganese / yttrium co-doped PMS-PZT piezoelectric ceramic materials. The method of preparing materials by manganese / yttrium co-doping can control the electrical properties and domain structure of the materials, thereby improving the high-temperature piezoelectric properties of the materials.

[0033] The technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only a part of the embodiments of this application, and not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of this application without creative effort are within the scope of protection of this application.

[0034] It should be noted that the terms "first," "second," etc., in the specification, claims, and accompanying drawings of this application are used to distinguish similar objects and are not necessarily used to describe a specific order or sequence. It should be understood that such data can be interchanged where appropriate so that the embodiments of this application described herein can be implemented in orders other than those illustrated or described herein. Furthermore, the terms "comprising" and "having," and any variations thereof, are intended to cover non-exclusive inclusion; for example, a process, method, system, product, or apparatus that comprises a series of steps or units is not necessarily limited to those steps or units explicitly listed, but may include other steps or modules not explicitly listed or inherent to such processes, methods, products, or apparatus.

[0035] Example 1:

[0036] This application discloses a method for preparing piezoelectric ceramic materials (PMS-PZT) by co-doping with manganese yttrium, the preparation method of which is as follows (the preparation flow chart is shown in the figure). Figure 1 (as shown)

[0037] S1, This study uses Pb(Mn) composition 1 / 3 Sb 2 / 3 )0.05 Zr 0.475 Ti 0.475 This study focuses on a ceramic system with O3 and an additional 0.3 wt% Mn3O4 / Y2O3 doping. Different samples were designed by varying the doping ratio of Mn3O4 to Y2O3 (with the total doping amount fixed at 0.3 wt%). Specific sample numbers and compositions are as follows: M... 0.15 Y 0.15 (Doped with 0.15 wt% Mn3O4 and 0.15 wt% Y2O3).

[0038] S2. Place the weighed mixed raw materials in a planetary ball mill and wet-mill at 350 r / min for 12 hours to ensure uniform mixing of all components. After milling, the slurry is dried, sieved, and pre-pressed. Then, it is placed in an alumina crucible and heated to 850℃ at a heating rate of 5℃ / min and held for 2 hours to complete the pre-synthesis of the perovskite main crystalline phase. The pre-fired block is crushed and ball-milled again for 12 hours to obtain refined ceramic powder.

[0039] S3. The powder, after secondary ball milling and drying, is passed through a 178 μm (approximately 80 mesh) sieve, followed by the addition of 5% (by mass) polyvinyl alcohol (PVA) binder for mixing and granulation. The granulated powder is then passed through a 60-mesh sieve to obtain particles with good flowability. The granulated powder is placed in a mold and pressed under a pressure of 100 MPa to form circular ceramic green bodies with a diameter of approximately 15.2 mm and a thickness of approximately 1.5 mm.

[0040] S4. The formed green body is heated to 550°C at a rate of 5°C / min and held for 3 hours to completely remove the PVA binder. Then, the green body after binder removal is placed in a crucible with ceramic atmosphere powder of the corresponding composition for sintering. The temperature is increased to 1130°C at a rate of 5°C / min and held at this temperature for 2 hours to complete solid-state sintering and obtain a dense ceramic sample.

[0041] S5. Thin the sintered ceramic sample to less than 1 mm, and apply silver paste as electrodes to its upper and lower surfaces by screen printing. Then, heat it at 800℃ for 2-10 minutes to allow the silver electrodes to form a strong bond with the ceramic surface.

[0042] The PMS-PZT material obtained in Example 1 was characterized. The X-ray diffraction (XRD) pattern of the PMS-PZT material in Example 1 is shown below. Figure 2 As shown.

[0043] Example 2

[0044] The difference between Example 2 and Example 1 is that the doping ratio of Mn3O4 and Y2O3 is different in step S1. The doping ratio of Mn3O4 to Y2O3 is adjusted from (0.15%wt of manganese + 0.15%wt of yttrium) to (0.2%wt of manganese + 0.1%wt of yttrium). The rest is exactly the same as in Example 1, and the product is denoted as M. 0.2 Y 0.1 .

[0045] Example 3

[0046] The difference between Example 3 and Example 1 is that the doping ratio of Mn3O4 and Y2O3 is different in step S1. The doping ratio of Mn3O4 to Y2O3 is adjusted from (0.15%wt of manganese + 0.15%wt of yttrium) to (0.3%wt of yttrium). The rest is exactly the same as in Example 1, and the product is denoted as MOY. 0.3 .

[0047] Example 4

[0048] The difference between Example 4 and Example 1 is that the doping ratio of Mn3O4 and Y2O3 is different in step S1. The doping ratio of Mn3O4 to Y2O3 is adjusted from (0.15%wt of manganese + 0.15%wt of yttrium) to (0.1%wt of manganese + 0.2%wt of yttrium). The rest is exactly the same as in Example 1, and the product is denoted as M. 0.1 Y 0.2 .

[0049] Example 5

[0050] The difference between Example 5 and Example 1 is that the doping ratio of Mn3O4 and Y2O3 is different in step S1. The doping ratio of Mn3O4 to Y2O3 is adjusted from (0.15%wt of manganese + 0.15%wt of yttrium) to (0.3%wt of manganese). The rest is exactly the same as in Example 1, and the product is denoted as M. 0.3 Y0.

[0051] The PMS-PZT material prepared in the above embodiments was characterized. The X-ray diffraction (XRD) pattern of the PMS-PZT material is shown below. Figure 2 As shown.

[0052] XRD analysis showed that the Mn-Y co-doped PMS-PZT ceramics prepared in the five examples all maintained the perovskite structure, exhibiting typical MPB characteristics of coexistence of rhombohedral and tetragonal phases. Among them, M 0.2 Y 0.1 and M 0.15 Y 0.15 The two ratios can effectively stabilize the MPB structure and are conducive to obtaining excellent overall performance, while excessive Y doping may lead to a decrease in piezoelectric performance.

[0053] Figure 3 The images show cross-sectional SEM images of manganese-yttrium co-doped PMS-PZT, with compositions of (a) Mn / Y = 3 / 0, (b) Mn / Y = 2 / 1, (c) Mn / Y = 1.5 / 1.5, (d) Mn / Y = 1 / 2, (e) Mn / Y = 0 / 3, and (f) showing the changes in grain size and density with composition.

[0054] SEM results show that the ceramic grain size first increases and then decreases under different doping ratios. Pure phase and Mn-doped (Mn...) 0.3 The Y0 sample has a small grain size (approximately 3.52 μm) and contains an appropriate amount of Mn. 2+ Doping can accelerate grain growth by promoting oxygen vacancy formation; and with the increase of Y... 3+ Increased doping concentration (e.g., M) 0.1 Y 0.2 and M0Y 0.3 The grain size gradually decreases (to approximately 3.16 μm), which is due to the Y... 3+ The lattice distortion caused by substitution and the pinning effect of oxygen vacancies on grain boundaries inhibit grain growth.

[0055] Figure 4 The graph shows the Curie temperature of ceramic samples as a function of doping ratio. The study indicates that the doping ratio significantly affects the Curie temperature (T0). C It has a significant regulatory effect, and single Mn doping (M 0.3 Y0) will reduce T C Appropriate co-doping (such as M) 0.15 Y 0.15 ) or high Y doping (MOY) 0.3 Then T can be used C The temperature was significantly increased to over 330°C, indicating that its synergistic doping can effectively enhance the high-temperature stability of the material.

[0056] Figure 5 The electrical performance parameters of the manganese-yttrium co-doped PMS-PZT piezoelectric ceramic samples are shown. Different Mn-Y co-doping ratios significantly modulate the overall electrical properties of PMS-PZT ceramics. The piezoelectric constant (d...) 33 ) with Y 3+ M0Y increases with increasing doping. 0.3 The highest concentration of the component indicates that Y 3+ It can effectively enhance polarization ability. Appropriate Mn-Y co-doping (such as Mn-Y) 0.15 Y 0.15 ) can further improve d 33 Electromechanical coupling coefficient (k) p In M 0.15 Y 0.15The fact that the composition reached its peak indicates that appropriate co-doping can optimize the domain structure and improve the electromechanical conversion efficiency, while single Mn doping (M 0.3 Y0) or excessive Y doping (MOY) 0.3 All of these will cause k p Decrease. Dielectric constant (ε) r The increase was significant in the Mn-Y co-doped samples, indicating that Y 3+ Doping enhances dielectric polarization. Dielectric loss (tanδ) can be reduced by appropriate co-doping (such as M). 0.15 Y 0.15 ) was optimized, but Y was excessive (M0Y) 0.3 This can lead to an increase in tanδ, which may impair high-power stability.

[0057] Figure 6 M in the example 0.15 Y 0.15 The piezoelectric constant d of the ceramic sample after polarization at 270℃ 33 The curve showing the change of M over time can be seen. 0.15 Y 0.15 It can maintain piezoelectric constant stability for 10 days at a Curie temperature of 270°C.

[0058] Conclusion: Stable quasi-isomorphic phase boundary (MPB) structure (M 0.15 Y 0.15 This can improve the polarization ability and temperature stability of materials, and increase the Y content. 3+ Doping (M0Y3) causes the structure to shift towards the rhombohedral phase, reducing the piezoelectric response. Manganese-yttrium co-doping can optimize grain growth and sintering density, and effectively control oxygen vacancy concentration. Appropriate oxygen vacancies enhance domain wall mobility and improve polarization reversal capability, while excessive oxygen vacancies easily lead to enhanced domain wall pinning, affecting polarization reversibility. High Y... 3+ Doping (M0Y3) may weaken the degrees of freedom of polarization domains and reduce piezoelectric properties. Piezoelectric and dielectric property test results show that co-doping with manganese yttrium can improve d... 33 k p This reduces dielectric loss and optimizes the material's high power adaptability and wide temperature range stability. Long-term stability tests show that M... 0.15 Y 0.15 It can maintain piezoelectric constant stability for 10 days at a Curie temperature of 270°C.

[0059] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the technical principles of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A wide-temperature-range manganese yttrium co-doped PMS-PZT piezoelectric ceramic material, characterized in that: The wide-temperature-range manganese-yttrium co-doped PMS-PZT piezoelectric ceramic material is made by doping 0.25~0.35wt% Mn3O4 / Y2O3 into PMS-PZT ceramic, wherein the weight ratio of Mn3O4 / Y2O3 is (3~0):(0~3).

2. The wide-temperature-range manganese yttrium co-doped PMS-PZT piezoelectric ceramic material according to claim 1, characterized in that: The PMS-PZT ceramic has a composition of Pb(Mn) 1 / 3 Sb 2 / 3 ) 0.05 Zr 0.475 Ti 0.475 The doping amount of O3, Mn3O4 / Y2O3 is 0.3wt%, and the ratio of Mn3O4 / Y2O3 is 1:

1.

3. A method for preparing a wide-temperature-range manganese yttrium co-doped PMS-PZT piezoelectric ceramic material according to claim 1 or 2, characterized in that... Includes the following steps: 1) Weigh the Pb3O4, TiO2, ZrO2, Mn3O4, Sb3O4, and Y2O3 powders according to a certain stoichiometric ratio, and then place them in a planetary ball mill to ball mill until they are mixed evenly. 2) After the ball milling slurry is dried, sieved, and pre-pressed, it is placed in an alumina crucible and heated to the reaction temperature of 400-1200℃ at a rate of 2-10℃ / min. The temperature is maintained for 1-5 hours to pre-synthesize ceramic powder. Then, it is crushed and further ball milled to obtain fine ceramic powder. 3) After the ceramic powder is ball-milled and dried twice, it is sieved, an appropriate amount of polyvinyl alcohol binder is added, mixed evenly and granulated. After granulation, it is sieved through a certain sieve and placed in a mold to be pressed into a round ceramic green body with a certain diameter and thickness. 4) The formed ceramic green body is heated to 500℃-800℃ at a rate of 1℃ / min-10℃ / min and held for 1h-5h to volatilize and remove the polyvinyl alcohol binder. The powder is then evenly spread and buried for firing. The temperature is then increased to 500℃-1500℃ at a rate of 1℃ / min-10℃ / min and held for 1h-10h for solid-state sintering to obtain the ceramic sample. 5) Thin the sintered ceramic sample to less than 2 mm, apply silver paste to its upper and lower surfaces as electrodes, and then heat it at 500℃-1000℃ for 2-10 min to allow the silver electrodes to bond tightly with the ceramic surface, thus obtaining the final ceramic sample.

4. The preparation method according to claim 3, characterized in that: The ball milling speed in step 1) is 300 r / min-600 r / min, and the ball milling time is 4-20 h.

5. The preparation method according to claim 3, characterized in that: In step 2), the ball milling speed is 300 r / min-600 r / min, and the ball milling time is 4-20 h.

6. The preparation method according to claim 3, characterized in that: The sieve particle size in step 3) is 50μm-300μm; the mass fraction of the added polyvinyl alcohol binder is 1%-10%, and it is sieved through a 20-100 mesh sieve after granulation.

7. The preparation method according to claim 3, characterized in that: The granulated and sieved powder from step 3) is placed in a mold and pressed into a circular ceramic green body with a diameter of about 15-16 mm and a thickness of about 1.4-1.6 mm under a pressure of 90-110 MPa.

8. The preparation method according to claim 3, characterized in that: Step 4) involves placing the ceramic green body after debinding into a crucible containing ceramic atmosphere powder of the corresponding components for firing.

9. The preparation method according to claim 3, characterized in that: In step 5), silver paste is applied to the upper and lower surfaces of the ceramic sample using screen printing.

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