CN112047756A - Method for improving electrical property of ferroelectric/piezoelectric ceramic material - Google Patents
Method for improving electrical property of ferroelectric/piezoelectric ceramic materialDownload PDFInfo
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Abstract
Description
Translated fromChinese技术领域technical field
本发明涉及一种提高铁电/压电陶瓷材料电学性能的方法，属于功能材料的铁电/压电陶瓷材料领域。The invention relates to a method for improving the electrical properties of ferroelectric/piezoelectric ceramic materials, and belongs to the field of ferroelectric/piezoelectric ceramic materials of functional materials.
背景技术Background technique
铁电/压电陶瓷材料作为一种重要的功能材料，在电、声、热、力和光传感和能量转换器件中发挥着重要的作用，广泛应用于电子信息技术、航空航天、无损检测、超声诊断和智能系统等高新技术领域。Ferroelectric/piezoelectric ceramic materials, as an important functional material, play an important role in electrical, acoustic, thermal, force and light sensing and energy conversion devices, and are widely used in electronic information technology, aerospace, non-destructive testing, Ultrasound diagnosis and intelligent systems and other high-tech fields.
铁电/压电陶瓷材料应用的基础是具有自发极化，且自发极化方向在外加电场作用下可以发生变化。众所周知，铁电/压电陶瓷材料获得所需的电学性能，通常需要通过施加电场的方法使铁电/压电陶瓷材料极化获得。极化是通过施加电场使铁电/压电陶瓷材料中的电畴反转取向一致的过程。只有在一定电场、一定温度和一定时间作用下，铁电畴沿着电场方向择优取向定向排列产生永久极化后，才具备宏观上的极化性能，对外显示出铁电、压电、热释电以及电光效应等。铁电畴的取向及与之相关的畴壁运动直接关系到铁电/压电陶瓷材料的介电、铁电、压电、热释电以及电光等宏观性能。The application of ferroelectric/piezoelectric ceramic materials is based on spontaneous polarization, and the direction of spontaneous polarization can be changed under the action of an external electric field. It is well known that the desired electrical properties of ferroelectric/piezoelectric ceramic materials are usually obtained by polarizing the ferroelectric/piezoelectric ceramic materials by applying an electric field. Polarization is the process of reversing the orientation of domains in a ferroelectric/piezoceramic material by applying an electric field. Only under the action of a certain electric field, a certain temperature and a certain time, the ferroelectric domains are permanently polarized by the preferential orientation and orientation of the electric field direction, and then they have macroscopic polarization properties, showing ferroelectric, piezoelectric, and pyroelectric properties to the outside world. electricity and electro-optic effects. The orientation of ferroelectric domains and the related domain wall motion are directly related to the dielectric, ferroelectric, piezoelectric, pyroelectric and electro-optical properties of ferroelectric/piezoceramic materials.
不同材料极化时所需要的极化电场、极化温度和极化时间大小差异很大。通常而言，极化电场需要高于矫顽场(EC)，EC是使铁电畴发生转向的临界电场，EC是极化电场的下限。然而，只有达到饱和极化后所呈现的性能，才能更好地满足应用。达到饱和极化状态所需要的饱和电场通常比矫顽场高3～4倍。另一方面，矫顽场和饱和电场都随着温度升高而降低，显然能在较高的温度下进行极化是有利的，但是高温条件下材料的绝缘电阻和击穿场强下降的很快，可能会发生介电击穿，因此击穿场强是极化电压的上限。极化时间取决于铁电畴热运动所需的能量与驱使铁电畴转向的驱动力的大小，前者与温度有关，后者与外加电场的大小有关。极化时间的长短可以根据极化电压的大小进行一些调节。在实际工作中，最佳的极化条件一般通过组合实验来探索获得，通常都是在一定的高温(几十～几百摄氏度)条件下，施加2～3倍于矫顽场的电场，保压合适的时间(几分钟～几个小时)。The polarization electric field, polarization temperature and polarization time required for polarization of different materials are very different. Generally speaking, the polarizing electric field needs to be higher than the coercive field (EC ), whereEC is the critical electric field for turning the ferroelectric domains, andEC is the lower limit of the polarizing electric field. However, only the performance presented after reaching saturation polarization can be better suited to the application. The saturation electric field required to reach the saturation polarization state is usually 3-4 times higher than the coercive field. On the other hand, both the coercive field and the saturation electric field decrease with the increase of temperature. Obviously, it is advantageous to be able to carry out polarization at higher temperature, but the insulation resistance and breakdown field strength of the material decrease very much at high temperature. Fast, dielectric breakdown may occur, so the breakdown field strength is the upper limit of the polarization voltage. The polarization time depends on the energy required for the thermal motion of the ferroelectric domain and the driving force driving the ferroelectric domain to turn. The former is related to the temperature, and the latter is related to the magnitude of the applied electric field. The length of the polarization time can be adjusted according to the polarization voltage. In practical work, the optimal polarization conditions are generally obtained through combined experiments. Usually, under a certain high temperature (tens to hundreds of degrees Celsius), an electric field 2 to 3 times the coercive field is applied to keep the Press for a suitable time (a few minutes to several hours).
在高温极化过程中，铁电畴运动活性增加，利于铁电畴(极化)反转，并同时降低矫顽场和饱和极化电场，更容易达到饱和极化状态。但是，在高温条件下，电场卸载后铁电畴的回转(backswitching)也是一个普遍的现象，铁电畴回转的程度和回转时间因材料各异，通常温度越高，电畴的回转程度越大。铁电畴的回转会造成电学性能的降低，这是铁电/压电陶瓷材料性能老化的一个方面原因。目前，本领域主要通过离子掺杂、固溶等组分设计或者通过制备工艺优化来获得性能优异的铁电/压电陶瓷材料。During the high-temperature polarization process, the motion activity of the ferroelectric domain increases, which is conducive to the reversal of the ferroelectric domain (polarization), and reduces the coercive field and the saturation polarization electric field at the same time, making it easier to reach the saturation polarization state. However, under high temperature conditions, the backswitching of the ferroelectric domain after the electric field is unloaded is also a common phenomenon. The degree and time of the ferroelectric domain rotation are different due to different materials. Generally, the higher the temperature, the greater the degree of rotation of the electric domain. . The rotation of the ferroelectric domain will cause the decrease of the electrical properties, which is one of the reasons for the aging of the properties of the ferroelectric/piezoceramic materials. At present, ferroelectric/piezoelectric ceramic materials with excellent performance are mainly obtained in this field through component design such as ion doping, solid solution, or through optimization of the preparation process.
发明内容SUMMARY OF THE INVENTION
针对上述问题，本发明旨在通过极化工艺的优化，实现铁电/压电陶瓷材料高温极化过程中铁电畴回转效应的弱化，提供一种提高铁电/压电陶瓷材料电学性能(如，剩余极化强度、压电常数、机电耦合系数等)的方法，将铁电/压电陶瓷材料进行第一次极化处理和第二次极化处理，以提升铁电/压电陶瓷材料的与电畴取向相关的电学性能；In view of the above-mentioned problems, the present invention aims to realize the weakening of the ferroelectric domain rotation effect in the high-temperature polarization process of the ferroelectric/piezoelectric ceramic material through optimization of the polarization process, and to provide a method for improving the electrical properties of the ferroelectric/piezoelectric ceramic material (such as , remanent polarization, piezoelectric constant, electromechanical coupling coefficient, etc.), the ferroelectric/piezoelectric ceramic material is subjected to the first polarization treatment and the second polarization treatment to improve the ferroelectric/piezoelectric ceramic material The electrical properties related to the domain orientation;
所述第一次极化处理的极化电场E1为(1～5)倍的EC，所述Ec为铁电/压电陶瓷材料的矫顽场；The polarization electric field E1 of the first polarization treatment is (1-5) times EC , and the Ec is the coercive field of the ferroelectric/piezoelectric ceramic material;
所述第二次极化处理的极化电场E2的方向与极化电场E1的方向相同，且E1≤E2＜Eb，Eb为铁电/压电陶瓷材料的击穿场强，且第二次极化处理的温度T2＜第一次极化处理的温度T1。The direction of the polarization electric field E2 of the second polarization treatment is the same as the direction of the polarization electric field E1 , and E1 ≤E2 <Eb , Eb is the breakdown field of the ferroelectric/piezoelectric ceramic material is strong, and the temperature T2 of the second polarization treatment < the temperature T1 of the first polarization treatment.
在本公开中，沿着第一次极化处理的极化电场E1的方向再次施加极化电场E2，并控制E1≤E2＜Eb(Eb为铁电/压电陶瓷材料的击穿场强)且第二次极化处理的温度T2＜第一次极化处理的温度T1，在该条件下第二次极化处理的铁电畴的回转远低于第一次极化处理的过程，从极化工艺优化上使得铁电/压电陶瓷材料中在第一次高温极化处理后电场E1卸载时发生和回转(backswitching)的部分铁电畴沿着第二次极化处理方向(极化电场E2)重新取向，以得到了性能优异的铁电/压电陶瓷材料。In the present disclosure, the polarization electric field E2 is reapplied along the direction of the polarization electric field E1 of the first polarization treatment, and E1 ≤ E2 <Eb (Eb is a ferroelectric/piezoelectric ceramic material) The breakdown field strength) and the temperature T2 of the second polarization treatment < the temperature T1 of the first polarization treatment, under this condition, the rotation of the ferroelectric domain of the second polarization treatment is much lower than that of the first polarization treatment. The process of sub-polarization treatment, from the optimization of the polarization process, makes some ferroelectric domains in the ferroelectric/piezoelectric ceramic material that occur when the electric field E1 is unloaded after the first high-temperature polarization treatment and are backswitched along the first stage. The direction of the secondary polarization treatment (polarization electric field E2 ) is re-oriented to obtain a ferroelectric/piezoelectric ceramic material with excellent performance.
较佳的，所述第二次极化处理的温度T2为10～50℃，例如室温范围，优选15～30℃。Preferably, the temperature T2 of thesecond polarization treatment is 10-50°C, for example, in the range of room temperature, preferably 15-30°C.
较佳的，所述第一次极化处理的时间为5～30分钟。Preferably, the time for the first polarization treatment is 5-30 minutes.
较佳的，所述第二次极化处理的时间为1～60秒。Preferably, the time for the second polarization treatment is 1 to 60 seconds.
较佳的，所述铁电/压电陶瓷材料为PZT压电陶瓷、PZST铁电陶瓷、BaTiO3基压电陶瓷或经过改性或者固溶获得的类似陶瓷体系。所述的铁电/压电陶瓷材料包括常见的铁电/压电陶瓷材料体系及其元器件，存在形式可以是单晶、陶瓷、薄膜、厚膜或者是多层元器件。Preferably, the ferroelectric/piezoelectric ceramic materials are PZT piezoelectric ceramics, PZST ferroelectric ceramics, BaTiO3 based piezoelectric ceramics or similar ceramic systems obtained by modification or solid solution. The ferroelectric/piezoelectric ceramic materials include common ferroelectric/piezoelectric ceramic material systems and components thereof, and the existing forms may be single crystal, ceramics, thin films, thick films or multi-layer components.
较佳的，所述第一次极化处理和第二次极化处理的极化环境为油浴环境、空气气氛或真空气氛。Preferably, the polarization environment for the first polarization treatment and the second polarization treatment is an oil bath environment, an air atmosphere or a vacuum atmosphere.
另一方面，本发明还提供了一种根据上述的方法制备的铁电/压电陶瓷材料。On the other hand, the present invention also provides a ferroelectric/piezoelectric ceramic material prepared according to the above method.
有益效果：Beneficial effects:
采用本发明所述方法可以弱化铁电/压电陶瓷材料高温极化时发生的铁电畴回转效应，与未经二次极化处理的材料相比，处理后的铁电/压电陶瓷材料与畴取向有关的电学性能可获得一定程度的提高。该工艺方法可操作性强，效果明显，可以用于铁电/压电陶瓷材料的工程化生产。The method of the invention can weaken the ferroelectric domain rotation effect that occurs when the ferroelectric/piezoelectric ceramic material is polarized at high temperature. Compared with the material without secondary polarization treatment, the treated ferroelectric/piezoelectric ceramic material The electrical properties related to domain orientation can be improved to some extent. The process method has strong operability and obvious effect, and can be used for the engineering production of ferroelectric/piezoelectric ceramic materials.
具体实施方式Detailed ways
以下通过下述实施方式进一步说明本发明，应理解，下述实施方式仅用于说明本发明，而非限制本发明。The present invention is further described below through the following embodiments, and it should be understood that the following embodiments are only used to illustrate the present invention, but not to limit the present invention.
在本公开中，旨在通过极化工艺的优化，实现铁电/压电陶瓷材料高温极化过程中电场卸载后回转的部分铁电畴重新取向，提供一种提高铁电/压电陶瓷材料电学性能的极化方法。具体来说，通过将铁电/压电陶瓷材料进行两次极化处理，以提升所述铁电/压电陶瓷材料与电畴取向相关的电学性能，如剩余极化强度、压电常数、机电耦合系数等。In the present disclosure, the aim is to realize the reorientation of part of the ferroelectric domains that are rotated after the electric field is unloaded during the high-temperature polarization process of the ferroelectric/piezoelectric ceramic material through the optimization of the polarization process, and provide a kind of improved ferroelectric/piezoelectric ceramic material. Polarization method for electrical properties. Specifically, by subjecting the ferroelectric/piezoelectric ceramic material to two polarization treatments, the electrical properties of the ferroelectric/piezoelectric ceramic material related to the electrical domain orientation, such as remanent polarization, piezoelectric constant, Electromechanical coupling coefficient, etc.
以下示例性地说明提高铁电/压电陶瓷材料的电学性能的方法。The method for improving the electrical properties of the ferroelectric/piezoelectric ceramic material is exemplified below.
通常，在合适的极化条件下，对铁电/压电陶瓷材料进行第一次极化处理，以使其达到饱和极化效果，即，其饱和极化效果应当使陶瓷获得较佳的电学性能。其中，第一次极化处理所施加的极化电场E1的方向为所需获得性能的方向，通常为直流电场，可以是连续的、间断的或变强度的，大小为(1～5)EC，Ec为所述铁电/压电陶瓷材料的矫顽场。第一次极化处理的温度T1高于室温(50～200℃)、低于铁电/压电陶瓷材料的居里点TC，通常在几十～几百摄氏度，通过第一次极化处理，使样品达到饱和极化状态，较高电场强度和较长极化时间可以保证样品达到饱和状态。在第一次极化处理后，将样品温度自然降温至室温。Usually, under suitable polarization conditions, the ferroelectric/piezoelectric ceramic material is subjected to the first polarization treatment to make it achieve the saturation polarization effect, that is, the saturation polarization effect should enable the ceramic to obtain better electrical properties performance. Among them, the direction of the polarization electric field E1 applied in thefirst polarization treatment is the direction of the desired performance, which is usually a DC electric field, which can be continuous, discontinuous or variable intensity, and its size is (1 to 5) EC , Ec is the coercive field of the ferroelectric/piezoelectric ceramic material. The temperature T1 of the first polarization treatment is higher than room temperature (50-200°C) and lower than the Curie point TC of the ferroelectric/piezoelectric ceramic material, usually tens to hundreds of degrees Celsius. The sample reaches the saturation polarization state by chemical treatment, and the higher electric field intensity and longer polarization time can ensure that the sample reaches the saturation state. After the first polarization treatment, the sample temperature was naturally cooled to room temperature.
在可选的实施方式中，第一次极化处理的温度通常设定优选为50～200℃，极化时间优选可为10～30min。第一次极化优选电压为直流，电场强度E1通常优选为1.5～3Ec(例如2～4kV/mm)条件下进行。极化环境可以为油浴、空气环境或真空环境。In an optional embodiment, the temperature of the first polarization treatment is usually set to preferably 50-200° C., and the polarization time can preferably be 10-30 min. The voltage of the first polarization is preferably a direct current, and the electric field intensity E1 is generally preferably performed under the conditions of 1.5 to 3Ec (for example, 2 to 4 kV/mm). The polarized environment can be an oil bath, an air environment, or a vacuum environment.
然后沿第一次极化处理的方向对材料进行第二次极化处理，即第二次极化处理所施加的电场方向与第一极化电场方向相同。第二极化处理的作用就是抑制铁电压电陶瓷材料中铁电畴的backswitching(回转)，通过二次极化抑制电畴的回转来实现电学性能的提升。第二次极化处理应在更高的电场强度E2(电场幅值等于或者大于第一次极化电场E1，但应小于材料的击穿场强Eb。优选电场强度E2为陶瓷材料矫顽场Ec的2～5倍下进行，波形可以是连续的、间断的或变强度的，极化环境可以为油浴、空气环境或真空环境。第二次极化处理的温度T2低于T1，通常可优选为室温(例如15～30℃)，极化时间可长可短(优选仅需1～30秒)。极化环境可以为油浴、空气环境或真空环境。其中，第二次极化处理的极化效果是使铁电/压电陶瓷材料中在第一次高温极化电场卸载后发生回转(backswitching)部分的铁电畴沿着第一次极化处理的方向重新取向。Then, the material is subjected to a second polarization treatment along the direction of the first polarization treatment, that is, the direction of the electric field applied by the second polarization treatment is the same as the direction of the first polarization electric field. The function of the second polarization treatment is to suppress the backswitching (rotation) of the ferroelectric domain in the ferroelectric ceramic material, and the electrical performance is improved by suppressing the rotation of the electric domain through the secondary polarization. The second polarization treatment should be performed at a higher electric field strength E2 (the electric field amplitude is equal to or greater than the first polarization electric field E1 , but should be smaller than the breakdown field strength Eb of the material. Preferably, the electric field strength E2 is ceramic The material coercive field Ec is 2 to 5 times, the waveform can be continuous, intermittent or variable intensity, the polarization environment can be oil bath, air environment or vacuum environment. The temperature of the second polarization treatment T2 Below T1 , it is usually preferable to be room temperature (for example, 15 to 30° C.), and the polarization time can be long or short (preferably only 1 to 30 seconds). The polarization environment can be an oil bath, an air environment or a vacuum environment. Wherein , the polarization effect of the second polarization treatment is to make the ferroelectric domain of the ferroelectric/piezoelectric ceramic material in the backswitching part after the first high-temperature polarization electric field unload along the first polarization treatment Orientation reorientation.
其中，铁电/压电陶瓷材料包括常见的铁电/压电陶瓷材料体系及其元器件，存在形式可以是单晶、陶瓷、薄膜、厚膜或者是多层器件。Among them, ferroelectric/piezoelectric ceramic materials include common ferroelectric/piezoelectric ceramic material systems and their components, which can exist in the form of single crystals, ceramics, thin films, thick films or multi-layer devices.
在本公开中，采用上述方法可实现铁电/压电陶瓷材料(例如Pb(Zr,Ti)O3基或BaTiO3基铁电压电陶瓷材料、或将Pb(Zr,Ti)O3基或BaTiO3基铁电压电陶瓷材料经过改性或者固溶获得的对应陶瓷体系)在高温条件下极化电场卸载后铁电畴的回转部分重新取向。由于第二次极化温度显著低于第一次极化温度，极化电场高于第一次极化电场，该条件下铁电畴的回转远低于第一次极化过程。因此，与未经二次极化处理状态相比，该方法的效果使铁电压电陶瓷材料与电畴取向相关的电学性能均获得一定程度的提升。本发明是基于抑制铁电压电陶瓷材料中铁电畴的backswitching(回转)的思路，通过二次极化实现电学性能的提升。In the present disclosure, ferroelectric/piezoelectric ceramic materials (such as Pb(Zr,Ti)O3 -based or BaTiO3- based ferroelectric ceramic materials, or Pb(Zr,Ti)O3-based or Pb(Zr,Ti)O3 -based or BaTiO3- based ferroelectric piezoelectric ceramic materials are modified or obtained by solid solution corresponding ceramic systems) under high temperature conditions after the polarization electric field is unloaded, the rotating part of the ferroelectric domain is reoriented. Since the temperature of the second polarization is significantly lower than that of the first polarization, and the polarization electric field is higher than that of the first polarization, the rotation of the ferroelectric domain under this condition is much lower than that of the first polarization process. Therefore, compared with the state without secondary polarization treatment, the effect of this method makes the electrical properties related to the domain orientation of the ferroelectric ceramic material to be improved to a certain extent. The invention is based on the idea of suppressing the backswitching (rotation) of the ferroelectric domain in the ferroelectric ceramic material, and realizes the improvement of the electrical performance through the secondary polarization.
在本发明中，采用d33准静态测量仪测试铁电/压电陶瓷材料的压电常数d33。采用热退极化法测试铁电陶瓷材料的剩余极化强度Pr。采用谐振-反谐振法测试压电陶瓷材料的径向耦合系数kp。In the present invention, a d33 quasi-static measuring instrument is used to test the piezoelectric constant d33 of the ferroelectric/piezoelectric ceramic material. The remanent polarization Pr of the ferroelectric ceramic material was tested by thermal depolarization method. The radial coupling coefficient kp of piezoelectric ceramic materials was tested by the resonance-anti-resonance method.
下面进一步例举实施例以详细说明本发明。同样应理解，以下实施例只用于对本发明进行进一步说明，不能理解为对本发明保护范围的限制，本领域的技术人员根据本发明的上述内容作出的一些非本质的改进和调整均属于本发明的保护范围。下述示例具体的工艺参数等也仅是合适范围中的一个示例，即本领域技术人员可以通过本文的说明做合适的范围内选择，而并非要限定于下文示例的具体数值。下述实施例中若无特殊说明，室温一般指的是25℃。The following further examples are given to illustrate the present invention in detail. It should also be understood that the following examples are only used to further illustrate the present invention, and should not be construed as limiting the protection scope of the present invention. Some non-essential improvements and adjustments made by those skilled in the art according to the above content of the present invention belong to the present invention. scope of protection. The specific process parameters and the like in the following examples are only an example of a suitable range, that is, those skilled in the art can make selections within the suitable range through the description herein, and are not intended to be limited to the specific numerical values exemplified below. Unless otherwise specified in the following examples, the room temperature generally refers to 25°C.
实施例1Example 1
(1)在电场强度3kV/mm，100℃油浴条件下，将块状Pb0.99(Zr0.95Ti0.05)0.98Nb0.02O3(PZT95/5)铁电陶瓷样品(厚度2mm)极化10分钟，完成第一次极化处理，取出样品，冷却至室温；(1) The bulk Pb0.99 (Zr0.95 Ti0.05 )0.98 Nb0.02 O3 (PZT95/5) ferroelectric ceramic sample (thickness 2mm) was polarized for 10 minutes under the condition of electric field strength 3kV/mm and 100℃ oil bath , complete the first polarization treatment, take out the sample, and cool it to room temperature;
(2)将样品沿第一次极化处理电场的方向，在室温(～25℃)、4kV/mm电场下进行第二次极化处理，极化时间为5秒钟；(2) The sample is subjected to the second polarization treatment along the direction of the first polarization treatment electric field at room temperature (~25°C) and a 4kV/mm electric field, and the polarization time is 5 seconds;
(3)取两次极化处理后的样品和第一次极化处理状态样品，测试其相关的电学性能，具体数值如表1所示，PZT95/5铁电陶瓷的纵向压电常数d33和剩余极化强度均增加。(3) Take the samples after two polarization treatments and the samples in the state of the first polarization treatment, and test their related electrical properties. The specific values are shown in Table 1. The longitudinal piezoelectric constant d33 of PZT95/5 ferroelectric ceramics and remanent polarization.
实施例2Example 2
(1)在电场强度3kV/mm，100℃油浴条件下，将Pb0.99(Zr0.81Sn0.14Ti0.05)0.98Nb0.02O3(PZST)铁电陶瓷样品(厚度1mm)极化10分钟，完成第一次极化处理，取出样品，冷却至室温；(1) The Pb0.99 (Zr0.81 Sn0.14 Ti0.05 )0.98 Nb0.02 O3 (PZST) ferroelectric ceramic sample (thickness 1mm) was polarized for 10 minutes under the condition of an electric field strength of 3kV/mm and a 100°C oil bath, and completed For the first polarization treatment, take out the sample and cool it to room temperature;
(2)将样品沿第一次极化处理电场的方向，在室温(～25℃)、3.5kV/mm电场下进行第二次极化处理，极化时间为5分钟；(2) The sample is subjected to the second polarization treatment along the direction of the first polarization treatment electric field at room temperature (~25°C) and an electric field of 3.5kV/mm, and the polarization time is 5 minutes;
(3)取两次极化处理后的样品和第一次极化处理状态样品，测试其相关的电学性能，具体数值如表2所示，PZST铁电陶瓷的纵向压电常数d33和剩余极化强度均增加。(3) Take the samples after two polarization treatments and the samples in the first polarization treatment state, and test their related electrical properties. The specific values are shown in Table 2. The longitudinal piezoelectric constant d33 of PZST ferroelectric ceramics and the residual The polarization strength is increased.
实施例3Example 3
(1)在电场强度2.5kV/mm，90℃空气环境下，将块状PZT-5H压电陶瓷样品(厚度1mm)极化15分钟，完成第一次极化处理，取出样品，冷却至室温；(1) The bulk PZT-5H piezoelectric ceramic sample (thickness 1mm) was polarized for 15 minutes under the electric field strength of 2.5kV/mm and 90°C air to complete the first polarization treatment, and the sample was taken out and cooled to room temperature ;
(2)将样品沿第一次极化处理电场的方向，在室温(～25℃)、3.5kV/mm电场下进行第二次极化处理，极化时间为60秒钟；(2) The sample is subjected to the second polarization treatment along the direction of the first polarization treatment electric field at room temperature (~25°C) and an electric field of 3.5kV/mm, and the polarization time is 60 seconds;
(3)取两次极化处理后的样品和第一次极化处理状态样品，测试其相关的电学性能，具体数值如表3所示，PZT-5H压电陶瓷纵向压电常数d33和kp均增加。(3) Take the samples after two polarization treatments and the samples in the first polarization treatment state, and test their related electrical properties. The specific values are shown in Table 3. The longitudinal piezoelectric constants ofPZT -5H piezoelectric ceramics are kp increased.
实施例4Example 4
(1)在电场强度3kV/mm，110℃空气环境下，将块状PZT-5铁电陶瓷样品(厚度1mm)极化10分钟，完成第一次极化处理，取出样品，冷却至室温；(1) Under the electric field strength of 3kV/mm and the air environment of 110°C, the bulk PZT-5 ferroelectric ceramic sample (thickness 1mm) was polarized for 10 minutes to complete the first polarization treatment, and the sample was taken out and cooled to room temperature;
(2)将样品沿第一次极化处理电场的方向，在室温(～25℃)、4kV/mm电场下进行第二次极化处理，极化时间为30秒钟；(2) The sample is subjected to the second polarization treatment along the direction of the first polarization treatment electric field at room temperature (~25°C) and a 4kV/mm electric field, and the polarization time is 30 seconds;
(3)取两次极化处理后的样品和第一次极化处理状态样品，测试其相关的电学性能，具体数值如表4所示，PZT-5压电陶瓷纵向压电常数d33和kp均增加。(3) Take the samples after two polarization treatments and the samples in the first polarization treatment state, and test their related electrical properties. The specific values are shown in Table 4. The longitudinal piezoelectric constants of PZT-5 piezoelectric ceramics d33 and kp increased.
实施例5Example 5
(1)在电场强度2kV/mm，140℃油浴条件下，将块状BaTiO3铁电陶瓷样品(厚度3mm)极化20分钟，完成第一次极化处理，取出样品，冷却至室温；(1) Under the condition of electric field strength 2kV/mm and 140℃ oil bath, the bulk BaTiO3 ferroelectric ceramic sample (thickness3mm ) was polarized for 20 minutes, the first polarization treatment was completed, the sample was taken out, and cooled to room temperature;
(2)将样品沿第一次极化处理电场的方向，在50℃下3.5kV/mm电场下进行第二次极化处理，极化时间为3分钟；(2) The sample is subjected to the second polarization treatment under the electric field of 3.5kV/mm at 50°C along the direction of the first polarization treatment electric field, and the polarization time is 3 minutes;
(3)取两次极化处理后的样品和第一次极化处理状态样品，测试其相关的电学性能，具体数值如表5所示，BT压电陶瓷纵向压电常数d33和kp均增加。(3) Take the samples after two polarization treatments and the samples in the state of the first polarization treatment, and test their related electrical properties. The specific values are shown in Table 5. The longitudinal piezoelectric constants d33 and kp of BT piezoelectric ceramics are both Increase.
表1：Table 1:
表2：Table 2:
表3：table 3:
表4：Table 4:
表5：table 5:
实施例6Example 6
本实施例6中方法和实施例1中类似，区别在于：第二极化处理参数包括：将样品沿第一次极化处理电场的方向，在室温、3kV/mm电场下进行第二次极化处理，极化时间为5秒钟；取两次极化处理后的样品和第一次极化处理状态样品，测试其相关的电学性能，具体数值如表1所示，PZT95/5铁电陶瓷的纵向压电常数d33和剩余极化强度均增加。The method in this embodiment 6 is similar to that in embodiment 1, except that the second polarization treatment parameters include: the sample is subjected to the second polarization treatment at room temperature and an electric field of 3kV/mm along the direction of the electric field of the first polarization treatment. The polarization time was 5 seconds; the samples after two polarization treatments and the samples in the first polarization treatment state were taken to test their related electrical properties. The specific values are shown in Table 1. PZT95/5 ferroelectric Both the longitudinal piezoelectric constantd33 and the remnant polarization of the ceramics increase.
表6：Table 6:
对比例1Comparative Example 1
本对比例1中方法和实施例1中类似，区别在于：第二极化处理参数包括：在电场强度3kV/mm，100℃油浴条件下，将第一次极化处理后的PZT95/5铁电陶瓷样品(厚度2mm)二次极化10分钟，其相关参数参照表7，其性能提升有限，原因是二次极化温度过高，铁电畴的活性较高，即使经过二次极化工艺处理，其回到室温时铁电畴还存在一定的backswitching，不利于性能提升。The method in this comparative example 1 is similar to that in Example 1, the difference is that: the second polarization treatment parameters include: under the condition of electric field strength 3kV/mm, 100 ℃ oil bath, the PZT95/5 after the first polarization treatment The ferroelectric ceramic sample (thickness 2mm) was subjected to secondary polarization for 10 minutes, and its related parameters were shown in Table 7. The performance improvement was limited because the secondary polarization temperature was too high and the activity of the ferroelectric domain was high. chemical process, there is still a certain backswitching in the ferroelectric domain when it returns to room temperature, which is not conducive to performance improvement.
表7：Table 7:
对比例2Comparative Example 2
本对比例2中方法和实施例1中类似，区别在于：将样品沿第一次极化处理电场的方向的相反方向，在室温、4kV/mm电场下进行第二次极化处理，极化时间为5秒钟，其相关参数参照表8。The method in this comparative example 2 is similar to that in Example 1, the difference is that: the sample is subjected to the second polarization treatment at room temperature under the electric field of 4kV/mm in the opposite direction of the electric field of the first polarization treatment, and the polarization treatment is carried out. The time is 5 seconds, and its related parameters refer to Table 8.
表8：Table 8:
Claims (8)
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114175304A (en)* | 2021-03-31 | 2022-03-11 | 宁德新能源科技有限公司 | A negative pole piece, an electrochemical device and an electronic device comprising the negative pole piece |
| CN114287071A (en)* | 2021-03-31 | 2022-04-05 | 宁德新能源科技有限公司 | Negative pole piece, lithium metal battery containing negative pole piece and electronic device |
| WO2024032650A1 (en)* | 2022-08-12 | 2024-02-15 | 桂林电子科技大学 | High-temperature polarization method for strip-shaped or rod-shaped piezoelectric ceramics |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104230333A (en)* | 2014-02-27 | 2014-12-24 | 中国科学院声学研究所 | High-temperature piezoelectric ceramic material and preparation method thereof |
| CN109037432A (en)* | 2018-07-24 | 2018-12-18 | 歌尔股份有限公司 | Piezoelectric element temperature-changing polarization device and method |
- 2020
- 2020-08-13CNCN202010810673.9Apatent/CN112047756A/enactivePending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104230333A (en)* | 2014-02-27 | 2014-12-24 | 中国科学院声学研究所 | High-temperature piezoelectric ceramic material and preparation method thereof |
| CN109037432A (en)* | 2018-07-24 | 2018-12-18 | 歌尔股份有限公司 | Piezoelectric element temperature-changing polarization device and method |
Non-Patent Citations (1)
| Title |
|---|
| 张玉龙主编: "《高技术复合材料制备手册》", 31 May 2003, 国防工业出版社* |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114175304A (en)* | 2021-03-31 | 2022-03-11 | 宁德新能源科技有限公司 | A negative pole piece, an electrochemical device and an electronic device comprising the negative pole piece |
| CN114287071A (en)* | 2021-03-31 | 2022-04-05 | 宁德新能源科技有限公司 | Negative pole piece, lithium metal battery containing negative pole piece and electronic device |
| CN114175304B (en)* | 2021-03-31 | 2024-08-20 | 宁德新能源科技有限公司 | Negative electrode plate, electrochemical device comprising same and electronic device |
| CN114287071B (en)* | 2021-03-31 | 2024-11-08 | 宁德新能源科技有限公司 | Negative electrode sheet, lithium metal battery and electronic device containing the negative electrode sheet |
| WO2024032650A1 (en)* | 2022-08-12 | 2024-02-15 | 桂林电子科技大学 | High-temperature polarization method for strip-shaped or rod-shaped piezoelectric ceramics |
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