铋基极性陶瓷中的非铁电性起源压电效应研究
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摘要
压电材料是一类可实现机械能和电能相互转换的功能材料,在滤波器、驱动器、谐振器、传感器、蜂鸣器和超声换能器等各种电子元器件中有着广泛地应用。常见的压电材料主要为压电单晶和多晶(陶瓷)材料。在压电材料中,压电陶瓷由于制备简单,生产成本较低,在实际应用中占据着十分重要的地位。传统的压电陶瓷也称为铁电陶瓷。普通陶瓷通常是各向同性的,结构上具有球面对称的特征,故不具有压电效应。但对含有铁电相的陶瓷而言,通过施加直流电场使铁电陶瓷的自发极化方向在电场作用下重新取向,陶瓷总体会出现沿外电场方向的宏观剩余极化。此时陶瓷就具有了压电性。铁电陶瓷在一定条件下表现出电滞回线,其物理基础是可翻转的自发极化。
在目前应用的压电材料中,锆钛酸铅(PZT)因其优异的压电性能以及组分的可调节性而获得了最广泛地应用,并一直占据着压电材料的主要市场。但是,PZT的制备需要使用大量的含铅氧化物作为原料,在生产、使用及废弃后处理过程中都会对环境造成严重影响。近几年来,随着人们环保意识的增强以及可持续发展的需求,环境友好型压电材料逐渐成为世界各国研究的重点。
在取代PZT方面,目前压电材料的研究主要集中在以下两个方面,一是压电材料的少铅或无铅化；二是探索研发新的压电材料。压电材料的少铅或无铅化主要是通过对传统的无铅压电材料如钛酸钡、铌酸盐、钛酸铋钠等进行掺杂、取代、改进制备工艺等来实现,以期改进后的特性能满足在某一些特定领域取代PZT的要求。但总的说来,目前无铅压电陶瓷的性能与PZT相比还有较大差距。而探索研发制备新的压电材料主要包括合成新的铁电压电材料和制备基于挠曲电效应的压电材料。其中基于挠曲电效应的压电材料的研究正逐渐成为热点,相关研究文章也在逐年增多。
近几年我们通过传统的制备工艺制备了一类在烧结完成后不需电场极化就具有压电性的非铁电性起源压电陶瓷(在相关文章里我们命名为flexoelectric-type polar ceramics)。与传统的铁电性压电陶瓷不同,这类陶瓷的宏观对称性需用低于6mm点群的三斜晶系来描述,而且并不要求烧结和降温过程中陶瓷内部必须含有铁电相,即排除了该极性来源于铁电性的可能性。即使陶瓷中含有铁电相,在远高于该铁电相居里温度的温度以上,也能观察到压电谐振信号。从材料构成的角度讲,该类非铁电性起源压电陶瓷是一种混相结构,其中必然存在丰富的异质界面。在充分调研挠曲电效应的基础上,我们认为该类陶瓷的压电性最有可能起源于界面处的挠曲电效应。与Cross报道的挠曲电效应研究不同,非铁电性起源压电陶瓷的压电性起源更可能类似于Lubomirsky报道的准非晶薄膜中由温度梯度引起的挠曲电极化。此外,和那些与挠曲电相关的低维薄膜极性材料相比,非铁电性起源压电陶瓷是一类块体极性材料。
由于我们认为非铁电性起源压电陶瓷的压电性起源和挠曲电效应有关,因此在绪论里作者对当前挠曲电效应的一些具有代表性的研究进行了回顾。同时,为了给出更直观的对比,作者先对传统压电材料(仅限无机材料)进行了概述,文中主要回顾了压电单晶和多晶、压电薄膜和极性玻璃陶瓷的一些特点。在回顾传统极性材料和挠曲电效应研究的基础上,绪论里作者对本论文研究的非铁电性起源压电陶瓷的发现及研究现状进行了概述。
在本论文中,作者对非铁电性起源压电陶瓷的发现、制备和研究进展都做了详细地介绍。目前的研究表明由钙钛矿结构或类钙钛矿结构和软铋矿结构构成的组分在具有自然极性的非铁电性起源压电陶瓷中占有非常重要的地位。本论文主要选取Na0.5Bi0.5TiO3基非铁电性起源压电陶瓷,SrTiO3基非铁电性起源压电陶瓷和Sr2Bi4Ti5O18基非铁电性起源压电陶瓷作为研究对象,并在不同的章节分别介绍了它们的结构和物性。此外,文中还简单介绍了一类不含Bi12TiO20相的非铁电压电陶瓷,主要给出了其压电物性研究。
非铁电性起源压电陶瓷的发现源于研究传统Na0.5Bi0.5TiO3基无铅压电陶瓷过程中的一次失误,而最初的研究也是主要围绕Na2O-Bi2O3-TiO2体系的非铁电性起源压电陶瓷展开的。论文第三章主要研究了通过传统的制备工艺制备的Na0.5Bi0.5TiO3基非铁电性起源压电陶瓷。第三章的研究分为两个部分。一是研究了如下组分：Na0.5Bio.5TiO3+xBi2O3(x=0.05,0.1,0.15,0.25,0.4,0.5,0.75,1)(简写为NBT-xB, x=0.05,0.1,0.15,0.25,0.4,0.5,0.75,1)。通过XRD确定了其物相结构均为Na0.5Bi0.5TiO3相和Bi12Ti020相。通过Agilent4294A阻抗分析仪和d33测试仪研究了其压电谐振响应。研究发现,随着x值的增大,其压电响应呈现逐渐增强的趋势；当x大于等于0.5时,d33max可达7～8pC/N。这说明可通过组分优化来提高非铁电性起源压电陶瓷的压电性。文中研究了不同x值的NBT-xB陶瓷的XPS图谱的变化规律,并对NBT-xB非铁电性起源压电陶瓷的压电性起源的可能做了描述。文中还通过XPS研究了不同烧结温度对NBT-0.4B样品压电性的影响。通过分析我们认为对于x值较小的组分,其压电性主要起源于界面中畸变了的Ti06八面体的部分有序排列,而且由于氧化铋添加量较少,使得陶瓷中最终生成的非晶相含量也较少。综合起来这些组分表现出的压电性则较小；而对于x值较大的组分而言,其压电性主要起源于界面中畸变了的Ti06八面体和BiO5多面体的部分有序排列,而且由于氧化铋添加量较多,使得陶瓷中最终生成的非晶相含量也较多。综合起来这些组分表现出较强的压电响应。二是对12(Na0.5Bio.5)1-x(Sr,Ba,Ca)xTiO3-Bi12TiO20(其中x=0.06,0.2,0.3,0.5,0.8,1)组分进行了简单研究,肯定了这类陶瓷的广泛存在性。
虽然Na0.5Bi0.5TiO3基非铁电性起源压电陶瓷的研究表明其反常压电性并不来源于铁电相,但铁电相的存在是否是构成该类陶瓷所必须的要素的问题仍然是一个疑问。而且研究这类非铁电性起源压电陶瓷压电性的起源时,铁电相的存在也会产生很多干扰。为了解决这个问题,在第四章我们选择12SrTiO3-Bi12TiO20的组分作为主要研究对象。论文第四章研究的组分如下：12(Na0.5Bi0.5)1-XSrxTiO3-Bi12TiO20(x=0.2,0.3,0.5,1).作者首先通过XRD确定了这些组分的物相结构均为含SrTiO3的钙钛矿相和Bi12TiO20相,并研究了它们的压电物性。然后选取了12SrTiO3-Bi12TiO20的组分(简写为ST-BT)为主要研究对象。实现结果表明,非铁电性起源压电陶瓷压电性的起源不依赖于陶瓷中是否含有铁电相,肯定了ST-BT铁电性起源压电陶瓷是研究非铁电性起源压电陶瓷压电性起源的理想材料。通过X射线光电子能谱、拉曼散射和正电子湮没的研究,我们认为ST-BT非铁电性起源压电陶瓷的极性起源和陶瓷中大量缺陷的产生有着密切的关联。通过电场极化研究和差热分析,我们认为Bi12TiO20相在形成这类非铁电性起源压电陶瓷的过程中起到了非常重要的作用。参照准非晶薄膜的研究,作者认为ST-BT非铁电性起源压电陶瓷压电性的起源极有可能源于界面非晶相中畸变了的Ti06八面体和Bi05多面体的部分取向,并简要分析了挠曲电极化的物理机制。
在第五章作者主要介绍了一类含铋层状结构的非铁电性起源压电陶瓷。其中选取了传统制备工艺制备的Sr2Bi4Ti5O18基非铁电性起源压电陶瓷为主要研究对象,研究组分如下：Sr2Bi4Ti5O18+2Bi2O3。文中通过XRD、SEM、XPS和介电压电测量对该压电陶瓷进行了研究。通过分析作者认为该类陶瓷的自然极性起源和前面报道的Na0.5Bi0.5TiO3基非铁电性起源压电陶瓷和SrTiO3基非铁电性起源压电陶瓷的类似,应该和陶瓷中大量缺陷的产生有关。此外,SrTiO3组分中Bi12TiO20相在自然极性起源中可能起到更重要的作用。
在第五章中还简单介绍了一类生成物中不含有Bi12TiO20相但依然能在未极化的条件下表现出压电性的非铁电性起源压电陶瓷。文中主要对Bi4Ti3O12+BiA1O3组分的压电性进行了介绍.研究发现其宏观对称性和Nao.5Bi0.5TiO3基非铁电性起源压电陶瓷和SrTiO3基非铁电性起源压电陶瓷的类似属于三斜晶系。目前对这类陶瓷的极性起源还没有更深地认识,有待于进一步的详细研究。
本论文的主要目的是介绍我们在该领域的研究工作,阐述我们对这类压电陶瓷的理解和认识。同时希望有兴趣的读者能参与到这个方向的研究中来。毕竟无论是从纯粹的科学研究(如重新认识极性的起源)的角度还是从未来的应用价值(如高温应用)的角度,这类材料都为我们提供了新的思路。
Piezoelectric materials is a kind of functional materials which can realize the energy transformation between mechanical energy and the electrical energy, and have been widely used in filters, motors, vibrators, sensors, buzzers and ultrasonic transducers. The common piezoelectric materials mainly contain piezoelectric single crystals and piezoelectric poly cry stals(also called piezoelectric ceramics). In particular, piezoelectric ceramics play an important role in application because of their relatively simple fabrication process and relatively low cost. Traditional piezoelectric ceramics are referred to as ferroelectric ceramics. The common ceramics are isotropic because of their spherical symmetry, and then does not exhibit piezoelectricity. However, for the ceramics containing ferroelectric phases, it can exhibit piezoelectricity by reorienting the spontaneous polarization along the applied electric field because the isotropic macroscopic symmetry was broken after a poling process. Ferroelectric ceramics can present hysteresis loop under some condition because of the reversion of spontaneous polarization.
Up to now, lead zirconate titanate(PZT) is the most widely used of all piezoelectric material due to their excellent piezoelectric properties and their adjusting ingredients, and dominate the market for piezoelectric materials. However, these Pb-based material using plenty of PbO as raw material in fabrication process will bring hazard to the environment in their fabrication, application and disposal process. In recent year, owning to the improvement of environmental consciousness and the demands of sustainable development, environment-friendly piezoelectric materials have caught much attention in many countries.
Overall, there are two routes to settle the problem of Pb hazard of PZT. The first route is to replace PZT with the lead-free or lead less piezoelectric materials, and the second one is to explore new piezoelectric materials. For the first route, doping,substitution and improving the fabrication technique will be used to improve the piezoelectric properties of the candidate piezoelectric materials, such as BaTiO3,(K,Na)NbO3, sodium bismuth titanate, in the hope that the improved properties can meet the requirement in particular field where PZT always had been used. Unfortunately, there is still a large gap in the piezoelectric properties between the candidate piezoelectric materials and PZT. For the second route, the exploration of new piezoelectric materials mainly contains exploration of new piezoelectric materials and fabrication of the flexoelectric-based piezoelectric materials. In particular, the flexoelectric-based piezoelectric materials has become the focus in recent years, and the amount of the published articles related to this field has increased gradually year by year.
Recently, we reported a new kind of piezoelectric ceramics named as non-ferroelectric piezoelectric ceramics(also named as flexoelectric-type polar ceramics in our published articles). These ceramics were fabricated by traditional solid state reaction method and could present piezoelectricity after sintered in furnace without any electric field poling process. The macroscopic symmetry of these ceramics should only be described as triclinic system, which is freshly different from that of ferroelectric ceramics (described as6mm point group). Moreover, ferroelectric phases would be not the essential element for fabrication of these ceramics. Even if these ceramics contain ferroelectric phases, piezoelectric response will be detected far above the Curie temperature of the ferroelectric phases. From the perspective of constituents, these ceramics are made up of heterogeneous phases, and then large amount of heterogeneous interface will exist. Base on our knowledge about the research on flexoelectric effect, we proposed that the unusual piezoelectricity in non-ferroelectric piezoelectric ceramics may rely on the flexoelectric effect at heterogeneous interface. Moreover, the flexoelectric effect in non-ferroelectric piezoelectric ceramics would be similar to that originating from the temperature gradient in quasi-amorphous films reported by lubomirsky, which are different from that reported by Cross. In addition, compared with those reported flexoelectric-related low-dimensional films, non-ferroelectric piezoelectric ceramics are bulk polar materials.
Since we considered the importance of the flexoelectric effect in determining the unusual piezoelectricity in non-ferroelectric piezoelectric ceramics, an overview of the representative flexoelectric effect research in recent years was carried out in the introduction of this dissertation. Meanwhile, to give a distinct comparison, an overview of traditional piezoelectric materials was also conducted where represented the features of piezoelectric single crystals and polycrystals, piezoelectric films and polar glass-ceramics. Based on these reviews, the introduction gave an general overview of the discovery of non-ferroelectric piezoelectric ceramics and the achievement at present.
In the text of this dissertation, a more detailed review of the discovery, fabrication and research achievement was undertaken. Currently, the samples containing perovskite phase and Bi12TiO20phase predominate the research of non-ferroelectric piezoelectric ceramics. In this dissertation, Na0.5Bi0.5TiO3-based, SrTiO3-based and Sr2Bi4Ti5O18-based non-ferroelectric piezoelectric ceramics were chosen as the study subjects, and their properties were presented in different chapters respectively. Besides, another kind of non-ferroelectric piezoelectric ceramics was introduced in this dissertation. These ceramics did not contain Bi12TiO20phase, and the dissertation only gave a brief review of their piezoelectric properties.
The discovery of non-ferroelectric piezoelectric materials was attribute to a mistake made in the process of fabricating traditional Na0.5Bi0.5TiO3-based lead-free piezoelectric materials, and the initial research on this field had been set focus on Na2O-Bi2O3-TiO2system to explore new non-ferroelectric piezoelectric materials. Chapter3gave details of properties of Na0.5Bi0.5TiO3-based non-ferroelectric piezoelectric materials prepared by traditional solid state reaction method. Overall, this chapter can be divided into two components. The first component was set focus on the Nao.5Bio.5Ti03+xBi2O3(x=0.05,0.1,0.15,0.25,0.4,0.5,0.75,1)(abbreviated as NBT-xB,x=0.05,0.1,0.15,0.25,0.4,0.5,0.75,1) system. XRD analysis indicated that all of as-sintered ceramics contained two main crystalline phases:Nao.5Bio.5Ti03phase and Bi12Ti02o phase. The piezoelectric response was studied by an Agilent4294A impedance analyzer and a d33meter. It had been found that the piezoelectric response became stronger by increasing x values; for the samples with x values above0.5, the piezoelectric coefficient could reached7～8pC/N. This suggested that one could improve the piezoelectricity by optimizing constituent. Besides, Chapter3dealt with the XPS analysis of the NBT-xB samples, and discussed the underlying mechanism of the origin of piezoelectricity in these ceramics. Additionally, the influence of sintering temperature was also evaluated in virtue of the XPS analysis of NBT-0.4B compositions. On the basis of the analysis of experimental results and the inspiration of lubomirsky's research, we tried to give our probably plausible interpretations to illustrate the different origin of piezoelectricity in NBT-xB samples. For those compositions with smaller x values, their piezoelectricity might mainly originate from the partial alignment of distorted TiO6octahedra in amorphous phase at interface. Moreover, relatively low-level content of excess Bi2O3, would result in comparatively low-level content of amorphous phase. Combining these two points, then it was not surprised for the relatively weak piezoelectric response for those samples. For those compositions with larger x values, their piezoelectricity might mainly originate from the partial alignment of distorted TiO6octahedra and BiOs polyhedra in amorphous phase at interface. Besides, relatively high-level content of excess Bi2O3would result in comparatively high-level content of amorphous phase. Then, on the contrary, these samples exhibited relatively strong piezoelectric response. The second component mainly referred to the exploration of non-ferroelectric piezoelectric materials and the12(Nao.5Bio.5)1-x(Sr,Ba,Ca)xTi03-Bi12Ti02o (x=0.06,0.2,0.3,0.5,0.8,1) compositions were chosen as study subject. This study confirmed that the anomalous piezoelectricity found in Na0.5Bi0.5TiO3-based non-ferroelectric piezoelectric materials would be not an isolated case.
Although the study of Na0.5Bi0.5TiO3-based non-ferroelectric piezoelectric ceramics suggested that the anomalous piezoelectricity did not originate from ferroelectric phases, whether the ferroelectric phase was the essential element or the key factor to fabricate these unusual ceramics was still a question. Moreover, the ferroelectric phase sensitive to ambient environment would bring interferences to the study of virtual piezoelectricity coming from the amorphous. In chapter4, we chose12SrTiO3-Bi12TiO20composition as the main study subject to solve this problem. In chapter4, the compositions chosen as study subject were as follow:12(Nao.5Bio.5)1-xSrxTi03-Bi12Ti02o(x=0.2,0.3,0.5,1). We identified their main crystalline phases as a perovskite phase and a Bi12TiO20phase and studied their piezoelectric properties. Then, we chosen the12SrTi03-Bi12Ti02o (abbreviated as ST-BT) composition as the main study subject. The study of ST-BT ceramics indicated that the ferroelectric phase was not the essential element to fabricate these unusual ceramics and confirmed that ST-BT ceramics would be an appropriate candidate in the study of non-ferroelectric piezoelectricity. By combination of XPS, raman spectroscopy and positron annihilation, we proposed that the origin of polarity in non-ferroelectric piezoelectric ceramics had a close relationship with the large amount of defects generating in the sintering process. By electric poling study and DSC analysis, we proposed that Bi12TiO210could have an important role in these non-ferroelectric piezoelectric ceramics. Inspired the research achievement of quasi-amorphous films, we proposed that the piezoelectricity in ST-BT ceramics originate from the partial alignment of distorted TiO6octahedra and BiO5polyhedra in amorphous phase at interface. At last, a probable flexoelectric-related polarization mechanism was briefly discussed where the comparison between quasi-amorphous films and non-ferroelectric piezoelectric ceramics was mentioned.
In chapter5, a kind of non-ferroelectric piezoelectric ceramics containing Aurivillius compounds was mentioned. Sr2Bi4Ti5O18-based non-ferroelectric piezoelectric ceramics prepared by solid state reaction method was chosen as the main study subject. These ceramics fabricated by using a nominal composition formula: Sr2Bi4Ti5O18+2Bi2O3were studied by XRD, SEM, XPS, dielectric and piezoelectric measurement. Based on these analysis, we suggested that the origin of Sr2Bi4Ti5O18-based non-ferroelectric piezoelectric ceramics was similar to that of Nao.5Bio.5Ti03-based and SrTiO3-based non-ferroelectric piezoelectric ceramics, which correlated with the generation of large amount of defects. In addition, Bi12TiO20might play a more important role in generating the anomalous piezoelectricity in Sr2Bi4Ti5O18-based non-ferroelectric piezoelectric ceramics
In chapter5another kind of piezoelectric ceramics were also mentioned. The main crystalline phase of these ceramics did not contain Bi12TiO20phase, but these ceramics also could exhibit piezoelectricity before applying an electric poling process. Chapter5only gave an overview of the piezoelectricity of Bi4Ti3012+BiA103composition. It was found that the macroscopic symmetry of these ceramics should be described as triclinic system, which is similar to that of Na0.5Bi0.5TiO3-based and SrTiO3-based non-ferroelectric piezoelectric ceramics. The mechanism of origin of the piezoelectricity in these ceramics was still unclear, and more works needed to be done.
The basic purpose of this dissertation is to present our works in this new field, and expound our acquaintance and understanding of these non-ferroelectric piezoelectric ceramics. Moreover, we wish people who take interest in these ceramics can participate in the research of this field. After all, these unusual ceramics provide us a freshly new way to review the development of piezoelectric materials either from the perspective of pure scientific research(for example, rethinking the intrinsic origin of polarity) or from the perspective of potential utilization value(for example, the potential value in high temperature application).
在目前应用的压电材料中,锆钛酸铅(PZT)因其优异的压电性能以及组分的可调节性而获得了最广泛地应用,并一直占据着压电材料的主要市场。但是,PZT的制备需要使用大量的含铅氧化物作为原料,在生产、使用及废弃后处理过程中都会对环境造成严重影响。近几年来,随着人们环保意识的增强以及可持续发展的需求,环境友好型压电材料逐渐成为世界各国研究的重点。
在取代PZT方面,目前压电材料的研究主要集中在以下两个方面,一是压电材料的少铅或无铅化；二是探索研发新的压电材料。压电材料的少铅或无铅化主要是通过对传统的无铅压电材料如钛酸钡、铌酸盐、钛酸铋钠等进行掺杂、取代、改进制备工艺等来实现,以期改进后的特性能满足在某一些特定领域取代PZT的要求。但总的说来,目前无铅压电陶瓷的性能与PZT相比还有较大差距。而探索研发制备新的压电材料主要包括合成新的铁电压电材料和制备基于挠曲电效应的压电材料。其中基于挠曲电效应的压电材料的研究正逐渐成为热点,相关研究文章也在逐年增多。
近几年我们通过传统的制备工艺制备了一类在烧结完成后不需电场极化就具有压电性的非铁电性起源压电陶瓷(在相关文章里我们命名为flexoelectric-type polar ceramics)。与传统的铁电性压电陶瓷不同,这类陶瓷的宏观对称性需用低于6mm点群的三斜晶系来描述,而且并不要求烧结和降温过程中陶瓷内部必须含有铁电相,即排除了该极性来源于铁电性的可能性。即使陶瓷中含有铁电相,在远高于该铁电相居里温度的温度以上,也能观察到压电谐振信号。从材料构成的角度讲,该类非铁电性起源压电陶瓷是一种混相结构,其中必然存在丰富的异质界面。在充分调研挠曲电效应的基础上,我们认为该类陶瓷的压电性最有可能起源于界面处的挠曲电效应。与Cross报道的挠曲电效应研究不同,非铁电性起源压电陶瓷的压电性起源更可能类似于Lubomirsky报道的准非晶薄膜中由温度梯度引起的挠曲电极化。此外,和那些与挠曲电相关的低维薄膜极性材料相比,非铁电性起源压电陶瓷是一类块体极性材料。
由于我们认为非铁电性起源压电陶瓷的压电性起源和挠曲电效应有关,因此在绪论里作者对当前挠曲电效应的一些具有代表性的研究进行了回顾。同时,为了给出更直观的对比,作者先对传统压电材料(仅限无机材料)进行了概述,文中主要回顾了压电单晶和多晶、压电薄膜和极性玻璃陶瓷的一些特点。在回顾传统极性材料和挠曲电效应研究的基础上,绪论里作者对本论文研究的非铁电性起源压电陶瓷的发现及研究现状进行了概述。
在本论文中,作者对非铁电性起源压电陶瓷的发现、制备和研究进展都做了详细地介绍。目前的研究表明由钙钛矿结构或类钙钛矿结构和软铋矿结构构成的组分在具有自然极性的非铁电性起源压电陶瓷中占有非常重要的地位。本论文主要选取Na0.5Bi0.5TiO3基非铁电性起源压电陶瓷,SrTiO3基非铁电性起源压电陶瓷和Sr2Bi4Ti5O18基非铁电性起源压电陶瓷作为研究对象,并在不同的章节分别介绍了它们的结构和物性。此外,文中还简单介绍了一类不含Bi12TiO20相的非铁电压电陶瓷,主要给出了其压电物性研究。
非铁电性起源压电陶瓷的发现源于研究传统Na0.5Bi0.5TiO3基无铅压电陶瓷过程中的一次失误,而最初的研究也是主要围绕Na2O-Bi2O3-TiO2体系的非铁电性起源压电陶瓷展开的。论文第三章主要研究了通过传统的制备工艺制备的Na0.5Bi0.5TiO3基非铁电性起源压电陶瓷。第三章的研究分为两个部分。一是研究了如下组分：Na0.5Bio.5TiO3+xBi2O3(x=0.05,0.1,0.15,0.25,0.4,0.5,0.75,1)(简写为NBT-xB, x=0.05,0.1,0.15,0.25,0.4,0.5,0.75,1)。通过XRD确定了其物相结构均为Na0.5Bi0.5TiO3相和Bi12Ti020相。通过Agilent4294A阻抗分析仪和d33测试仪研究了其压电谐振响应。研究发现,随着x值的增大,其压电响应呈现逐渐增强的趋势；当x大于等于0.5时,d33max可达7～8pC/N。这说明可通过组分优化来提高非铁电性起源压电陶瓷的压电性。文中研究了不同x值的NBT-xB陶瓷的XPS图谱的变化规律,并对NBT-xB非铁电性起源压电陶瓷的压电性起源的可能做了描述。文中还通过XPS研究了不同烧结温度对NBT-0.4B样品压电性的影响。通过分析我们认为对于x值较小的组分,其压电性主要起源于界面中畸变了的Ti06八面体的部分有序排列,而且由于氧化铋添加量较少,使得陶瓷中最终生成的非晶相含量也较少。综合起来这些组分表现出的压电性则较小；而对于x值较大的组分而言,其压电性主要起源于界面中畸变了的Ti06八面体和BiO5多面体的部分有序排列,而且由于氧化铋添加量较多,使得陶瓷中最终生成的非晶相含量也较多。综合起来这些组分表现出较强的压电响应。二是对12(Na0.5Bio.5)1-x(Sr,Ba,Ca)xTiO3-Bi12TiO20(其中x=0.06,0.2,0.3,0.5,0.8,1)组分进行了简单研究,肯定了这类陶瓷的广泛存在性。
虽然Na0.5Bi0.5TiO3基非铁电性起源压电陶瓷的研究表明其反常压电性并不来源于铁电相,但铁电相的存在是否是构成该类陶瓷所必须的要素的问题仍然是一个疑问。而且研究这类非铁电性起源压电陶瓷压电性的起源时,铁电相的存在也会产生很多干扰。为了解决这个问题,在第四章我们选择12SrTiO3-Bi12TiO20的组分作为主要研究对象。论文第四章研究的组分如下：12(Na0.5Bi0.5)1-XSrxTiO3-Bi12TiO20(x=0.2,0.3,0.5,1).作者首先通过XRD确定了这些组分的物相结构均为含SrTiO3的钙钛矿相和Bi12TiO20相,并研究了它们的压电物性。然后选取了12SrTiO3-Bi12TiO20的组分(简写为ST-BT)为主要研究对象。实现结果表明,非铁电性起源压电陶瓷压电性的起源不依赖于陶瓷中是否含有铁电相,肯定了ST-BT铁电性起源压电陶瓷是研究非铁电性起源压电陶瓷压电性起源的理想材料。通过X射线光电子能谱、拉曼散射和正电子湮没的研究,我们认为ST-BT非铁电性起源压电陶瓷的极性起源和陶瓷中大量缺陷的产生有着密切的关联。通过电场极化研究和差热分析,我们认为Bi12TiO20相在形成这类非铁电性起源压电陶瓷的过程中起到了非常重要的作用。参照准非晶薄膜的研究,作者认为ST-BT非铁电性起源压电陶瓷压电性的起源极有可能源于界面非晶相中畸变了的Ti06八面体和Bi05多面体的部分取向,并简要分析了挠曲电极化的物理机制。
在第五章作者主要介绍了一类含铋层状结构的非铁电性起源压电陶瓷。其中选取了传统制备工艺制备的Sr2Bi4Ti5O18基非铁电性起源压电陶瓷为主要研究对象,研究组分如下：Sr2Bi4Ti5O18+2Bi2O3。文中通过XRD、SEM、XPS和介电压电测量对该压电陶瓷进行了研究。通过分析作者认为该类陶瓷的自然极性起源和前面报道的Na0.5Bi0.5TiO3基非铁电性起源压电陶瓷和SrTiO3基非铁电性起源压电陶瓷的类似,应该和陶瓷中大量缺陷的产生有关。此外,SrTiO3组分中Bi12TiO20相在自然极性起源中可能起到更重要的作用。
在第五章中还简单介绍了一类生成物中不含有Bi12TiO20相但依然能在未极化的条件下表现出压电性的非铁电性起源压电陶瓷。文中主要对Bi4Ti3O12+BiA1O3组分的压电性进行了介绍.研究发现其宏观对称性和Nao.5Bi0.5TiO3基非铁电性起源压电陶瓷和SrTiO3基非铁电性起源压电陶瓷的类似属于三斜晶系。目前对这类陶瓷的极性起源还没有更深地认识,有待于进一步的详细研究。
本论文的主要目的是介绍我们在该领域的研究工作,阐述我们对这类压电陶瓷的理解和认识。同时希望有兴趣的读者能参与到这个方向的研究中来。毕竟无论是从纯粹的科学研究(如重新认识极性的起源)的角度还是从未来的应用价值(如高温应用)的角度,这类材料都为我们提供了新的思路。
Piezoelectric materials is a kind of functional materials which can realize the energy transformation between mechanical energy and the electrical energy, and have been widely used in filters, motors, vibrators, sensors, buzzers and ultrasonic transducers. The common piezoelectric materials mainly contain piezoelectric single crystals and piezoelectric poly cry stals(also called piezoelectric ceramics). In particular, piezoelectric ceramics play an important role in application because of their relatively simple fabrication process and relatively low cost. Traditional piezoelectric ceramics are referred to as ferroelectric ceramics. The common ceramics are isotropic because of their spherical symmetry, and then does not exhibit piezoelectricity. However, for the ceramics containing ferroelectric phases, it can exhibit piezoelectricity by reorienting the spontaneous polarization along the applied electric field because the isotropic macroscopic symmetry was broken after a poling process. Ferroelectric ceramics can present hysteresis loop under some condition because of the reversion of spontaneous polarization.
Up to now, lead zirconate titanate(PZT) is the most widely used of all piezoelectric material due to their excellent piezoelectric properties and their adjusting ingredients, and dominate the market for piezoelectric materials. However, these Pb-based material using plenty of PbO as raw material in fabrication process will bring hazard to the environment in their fabrication, application and disposal process. In recent year, owning to the improvement of environmental consciousness and the demands of sustainable development, environment-friendly piezoelectric materials have caught much attention in many countries.
Overall, there are two routes to settle the problem of Pb hazard of PZT. The first route is to replace PZT with the lead-free or lead less piezoelectric materials, and the second one is to explore new piezoelectric materials. For the first route, doping,substitution and improving the fabrication technique will be used to improve the piezoelectric properties of the candidate piezoelectric materials, such as BaTiO3,(K,Na)NbO3, sodium bismuth titanate, in the hope that the improved properties can meet the requirement in particular field where PZT always had been used. Unfortunately, there is still a large gap in the piezoelectric properties between the candidate piezoelectric materials and PZT. For the second route, the exploration of new piezoelectric materials mainly contains exploration of new piezoelectric materials and fabrication of the flexoelectric-based piezoelectric materials. In particular, the flexoelectric-based piezoelectric materials has become the focus in recent years, and the amount of the published articles related to this field has increased gradually year by year.
Recently, we reported a new kind of piezoelectric ceramics named as non-ferroelectric piezoelectric ceramics(also named as flexoelectric-type polar ceramics in our published articles). These ceramics were fabricated by traditional solid state reaction method and could present piezoelectricity after sintered in furnace without any electric field poling process. The macroscopic symmetry of these ceramics should only be described as triclinic system, which is freshly different from that of ferroelectric ceramics (described as6mm point group). Moreover, ferroelectric phases would be not the essential element for fabrication of these ceramics. Even if these ceramics contain ferroelectric phases, piezoelectric response will be detected far above the Curie temperature of the ferroelectric phases. From the perspective of constituents, these ceramics are made up of heterogeneous phases, and then large amount of heterogeneous interface will exist. Base on our knowledge about the research on flexoelectric effect, we proposed that the unusual piezoelectricity in non-ferroelectric piezoelectric ceramics may rely on the flexoelectric effect at heterogeneous interface. Moreover, the flexoelectric effect in non-ferroelectric piezoelectric ceramics would be similar to that originating from the temperature gradient in quasi-amorphous films reported by lubomirsky, which are different from that reported by Cross. In addition, compared with those reported flexoelectric-related low-dimensional films, non-ferroelectric piezoelectric ceramics are bulk polar materials.
Since we considered the importance of the flexoelectric effect in determining the unusual piezoelectricity in non-ferroelectric piezoelectric ceramics, an overview of the representative flexoelectric effect research in recent years was carried out in the introduction of this dissertation. Meanwhile, to give a distinct comparison, an overview of traditional piezoelectric materials was also conducted where represented the features of piezoelectric single crystals and polycrystals, piezoelectric films and polar glass-ceramics. Based on these reviews, the introduction gave an general overview of the discovery of non-ferroelectric piezoelectric ceramics and the achievement at present.
In the text of this dissertation, a more detailed review of the discovery, fabrication and research achievement was undertaken. Currently, the samples containing perovskite phase and Bi12TiO20phase predominate the research of non-ferroelectric piezoelectric ceramics. In this dissertation, Na0.5Bi0.5TiO3-based, SrTiO3-based and Sr2Bi4Ti5O18-based non-ferroelectric piezoelectric ceramics were chosen as the study subjects, and their properties were presented in different chapters respectively. Besides, another kind of non-ferroelectric piezoelectric ceramics was introduced in this dissertation. These ceramics did not contain Bi12TiO20phase, and the dissertation only gave a brief review of their piezoelectric properties.
The discovery of non-ferroelectric piezoelectric materials was attribute to a mistake made in the process of fabricating traditional Na0.5Bi0.5TiO3-based lead-free piezoelectric materials, and the initial research on this field had been set focus on Na2O-Bi2O3-TiO2system to explore new non-ferroelectric piezoelectric materials. Chapter3gave details of properties of Na0.5Bi0.5TiO3-based non-ferroelectric piezoelectric materials prepared by traditional solid state reaction method. Overall, this chapter can be divided into two components. The first component was set focus on the Nao.5Bio.5Ti03+xBi2O3(x=0.05,0.1,0.15,0.25,0.4,0.5,0.75,1)(abbreviated as NBT-xB,x=0.05,0.1,0.15,0.25,0.4,0.5,0.75,1) system. XRD analysis indicated that all of as-sintered ceramics contained two main crystalline phases:Nao.5Bio.5Ti03phase and Bi12Ti02o phase. The piezoelectric response was studied by an Agilent4294A impedance analyzer and a d33meter. It had been found that the piezoelectric response became stronger by increasing x values; for the samples with x values above0.5, the piezoelectric coefficient could reached7～8pC/N. This suggested that one could improve the piezoelectricity by optimizing constituent. Besides, Chapter3dealt with the XPS analysis of the NBT-xB samples, and discussed the underlying mechanism of the origin of piezoelectricity in these ceramics. Additionally, the influence of sintering temperature was also evaluated in virtue of the XPS analysis of NBT-0.4B compositions. On the basis of the analysis of experimental results and the inspiration of lubomirsky's research, we tried to give our probably plausible interpretations to illustrate the different origin of piezoelectricity in NBT-xB samples. For those compositions with smaller x values, their piezoelectricity might mainly originate from the partial alignment of distorted TiO6octahedra in amorphous phase at interface. Moreover, relatively low-level content of excess Bi2O3, would result in comparatively low-level content of amorphous phase. Combining these two points, then it was not surprised for the relatively weak piezoelectric response for those samples. For those compositions with larger x values, their piezoelectricity might mainly originate from the partial alignment of distorted TiO6octahedra and BiOs polyhedra in amorphous phase at interface. Besides, relatively high-level content of excess Bi2O3would result in comparatively high-level content of amorphous phase. Then, on the contrary, these samples exhibited relatively strong piezoelectric response. The second component mainly referred to the exploration of non-ferroelectric piezoelectric materials and the12(Nao.5Bio.5)1-x(Sr,Ba,Ca)xTi03-Bi12Ti02o (x=0.06,0.2,0.3,0.5,0.8,1) compositions were chosen as study subject. This study confirmed that the anomalous piezoelectricity found in Na0.5Bi0.5TiO3-based non-ferroelectric piezoelectric materials would be not an isolated case.
Although the study of Na0.5Bi0.5TiO3-based non-ferroelectric piezoelectric ceramics suggested that the anomalous piezoelectricity did not originate from ferroelectric phases, whether the ferroelectric phase was the essential element or the key factor to fabricate these unusual ceramics was still a question. Moreover, the ferroelectric phase sensitive to ambient environment would bring interferences to the study of virtual piezoelectricity coming from the amorphous. In chapter4, we chose12SrTiO3-Bi12TiO20composition as the main study subject to solve this problem. In chapter4, the compositions chosen as study subject were as follow:12(Nao.5Bio.5)1-xSrxTi03-Bi12Ti02o(x=0.2,0.3,0.5,1). We identified their main crystalline phases as a perovskite phase and a Bi12TiO20phase and studied their piezoelectric properties. Then, we chosen the12SrTi03-Bi12Ti02o (abbreviated as ST-BT) composition as the main study subject. The study of ST-BT ceramics indicated that the ferroelectric phase was not the essential element to fabricate these unusual ceramics and confirmed that ST-BT ceramics would be an appropriate candidate in the study of non-ferroelectric piezoelectricity. By combination of XPS, raman spectroscopy and positron annihilation, we proposed that the origin of polarity in non-ferroelectric piezoelectric ceramics had a close relationship with the large amount of defects generating in the sintering process. By electric poling study and DSC analysis, we proposed that Bi12TiO210could have an important role in these non-ferroelectric piezoelectric ceramics. Inspired the research achievement of quasi-amorphous films, we proposed that the piezoelectricity in ST-BT ceramics originate from the partial alignment of distorted TiO6octahedra and BiO5polyhedra in amorphous phase at interface. At last, a probable flexoelectric-related polarization mechanism was briefly discussed where the comparison between quasi-amorphous films and non-ferroelectric piezoelectric ceramics was mentioned.
In chapter5, a kind of non-ferroelectric piezoelectric ceramics containing Aurivillius compounds was mentioned. Sr2Bi4Ti5O18-based non-ferroelectric piezoelectric ceramics prepared by solid state reaction method was chosen as the main study subject. These ceramics fabricated by using a nominal composition formula: Sr2Bi4Ti5O18+2Bi2O3were studied by XRD, SEM, XPS, dielectric and piezoelectric measurement. Based on these analysis, we suggested that the origin of Sr2Bi4Ti5O18-based non-ferroelectric piezoelectric ceramics was similar to that of Nao.5Bio.5Ti03-based and SrTiO3-based non-ferroelectric piezoelectric ceramics, which correlated with the generation of large amount of defects. In addition, Bi12TiO20might play a more important role in generating the anomalous piezoelectricity in Sr2Bi4Ti5O18-based non-ferroelectric piezoelectric ceramics
In chapter5another kind of piezoelectric ceramics were also mentioned. The main crystalline phase of these ceramics did not contain Bi12TiO20phase, but these ceramics also could exhibit piezoelectricity before applying an electric poling process. Chapter5only gave an overview of the piezoelectricity of Bi4Ti3012+BiA103composition. It was found that the macroscopic symmetry of these ceramics should be described as triclinic system, which is similar to that of Na0.5Bi0.5TiO3-based and SrTiO3-based non-ferroelectric piezoelectric ceramics. The mechanism of origin of the piezoelectricity in these ceramics was still unclear, and more works needed to be done.
The basic purpose of this dissertation is to present our works in this new field, and expound our acquaintance and understanding of these non-ferroelectric piezoelectric ceramics. Moreover, we wish people who take interest in these ceramics can participate in the research of this field. After all, these unusual ceramics provide us a freshly new way to review the development of piezoelectric materials either from the perspective of pure scientific research(for example, rethinking the intrinsic origin of polarity) or from the perspective of potential utilization value(for example, the potential value in high temperature application).
引文
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