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MnO2掺杂(Ba0.99Ca0.02)(Ti0.98Zr0.01)O3陶瓷的制备和压电性

时间:2018-03-17 15:42:10 编辑:知网查重入口 www.cnkiid.cn

 

摘  要
近年来,人们对环境问题越来越看重。因此,无污染的压电材料研发是至关重要的。传统的Pb(Zr1-xTix)O3(PZT)等铅基压电陶瓷对环境污染较大,继续找到可以替代其的材料。BaTiO3(BT)基压电陶瓷因其介电常数较高,电学性能优异,故成为最有潜力替代PZT陶瓷的材料。然而,纯钛酸钡的居里温度约为120℃,限制了它在室温下的使用,单体形式的化合物的介电损耗和漏电流不能满足使用需求。因此,通常使用固溶或掺杂来改良其功能。为了改良钛酸钡陶瓷材料的使用领域,对陶瓷材料的电学性能作了整体的改革。目前,提高钛酸钡性能的方法主要有掺杂、高活性原料的选择和制备方法。
本文采用传统固相反应法制备陶瓷样品,研究MnO2掺杂量对(Ba0.99Ca0.02)(Ti0.98Zr0.01)O3陶瓷样品的微结构和电学性能的影响。研究结果表明所有样品均呈现四方-正交两相共存的纯钙钛矿结构,TC均在120℃左右,0.3 mol%MnO2掺杂的(Ba0.99Ca0.02)(Ti0.98Zr0.01)O3样品呈现出较高的剩余极化强度Pr=15.7μC/cm2,EC= 180V/mm,这可能是因为适量MnO2掺杂有利于晶粒生长,促进电畴的移动,d33=308pC/N, tanδ=1.04%, 该材料可用于存储器和变压器中。
 
 
关键词 BaTiO3;无铅压电陶瓷;离子掺杂;压电性能;居里温度;
 
 
 
 
Preparation and piezoelectric properties of MnO2 doped (Ba0.99Ca0.02) (Ti0.98Zr0.01) O3 ceramics
 
Abstract
In recent years, people are increasingly concerned about environmental issues. Therefore, the development of non-polluting piezoelectric materials is essential. The traditional lead-based piezoelectric ceramics such as Pb (Zr1-xTix) O3 (PZT) have great environmental pollution and continue to find the materials that can replace them. BaTiO3 (BT) -based piezoelectric ceramics have the potential to replace PZT ceramics because of their high dielectric constant and excellent electrical properties. However, the Curie temperature of barium titanate is about 120 ° C, limiting its application at room temperature. The dielectric loss and leakage current of the compound in monomer form can not meet the application requirements. Thus, solid solution or doping is commonly used to improve its performance. In order to improve the application of barium titanate ceramic materials, the electrical properties of ceramic materials have been improved overall. At present, the method of improving the performance of barium titanate mainly has the choice of doping and high active raw materials and the preparation method.
In this paper, the effects of MnO2 doping on the microstructure and electrical properties of (Ba0.99Ca0.02) (Ti0.98Zr0.01) O3 ceramic samples were studied by using the traditional solid state reaction method. The results show that all samples show (Ba0.99Ca0.02) (Ti0.98Zr0.01) O3 samples doped with 0.3 mol% MnO2 at a temperature of about 120 ℃, respectively, showed a high residual The polarization strength Pr = 15.7μC / cm2, EC = 180V / mm, which may be due to the appropriate MnO2 doping is conducive to grain growth, promote the movement of the domain, d33 = 308pC / N, tanδ = 1.04%, the material available In memory and transformers.
 
 
 
Keywords : BaTiO3;Lead-free piezoelectric;ion doping ;piezoelectric properties; Curie temperature.

 

前 言
在19世纪80年代,科学家们发觉了压电效应,即机械能转化为电能。此后,具有压电效应的压电材料被应用于高新技术领域以及人们的日常生活当中,具体而言,是用于换能器、传感器等电子设备中,其在科技发展和日常生活中扮演着十分重要的角色。
目前商用的压电材料主要是铅基压电陶瓷,比如Pb(Zr1-xTix)O3(PZT)等,相较于其他压电材料,其具有相当的统治力,由于其使用了位于准同型相界的组分是x=0.48附近的组分,使得铅基压电陶瓷具备了在准同型相界组分附近的较为良好的压电性能以及机电耦合性能。Pb(Zr1-xTix)O3(PZT)等这些准同型相界的铅基压电陶瓷的优势也很明显,其相较于其他压电材料,具有更为优秀的压电性能。并且在外部温度区间跨度较大时,它的压电性能也十分稳定,并没有太大的波动。另外,为了满足不同领域要求,可以通过改变铅基压电陶瓷的配方,来制备多种陶瓷材料。然而值得注意的是,在制备Pb(Zr1-xTix)O3(PZT)等铅基压电陶瓷时,通常需要进行高温烧结,此过程中会产生铅,这些铅会挥发到空气中,或者时混杂在废弃物中,人体摄入一定量的铅后会出现中毒等症状,危害周边人们的健康。欧盟等组织已经开始对含铅的压电材料进行限制,人们现在也在研制出能够替代现有含铅压电材料的无铅压电材料,以期将来能够使用这些相对无害的压电材料。
 目前具有钙钛矿结构的钛酸钡、钛酸铋钠、铌酸钾钠和铋层状结构无铅压电陶瓷是研讨较多的无铅压电陶瓷体系。在一般没有掺杂的情况下时,钛酸钡(BaTiO3)压电陶瓷的压电常数d33为190 p C/N 上下,其压电性能经过改良工艺和离子掺杂改性后还可以进一步加强,对于一些低端领域其对压电性能要求比较低,钛酸钡基压电陶瓷的压电性能完全足够其应用的需求。西安交通大学任晓兵等对于这一类材料的研究有着优异的成果,其制备的钛酸钡基的 Ba(Ti, Zr)O3-x(Ba, Ca)Ti O3和 Ba(Ti, Sn)O3-x(Ba, Ca)Ti 3压电陶瓷的压电性能有了重大突破,其压电常数 d33分别高达了 540p C/N 和620p C/N。这一成果进一步证明了通过离子的掺杂,钛酸钡基压电陶瓷的压电活性和影响陶瓷的居里温度都可以有效地改善。获取有利于实际生产的工艺步骤和具有优异性能的压电陶瓷材料也可以通过优化制备工艺来实现

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