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High Performance Lead--free Piezoelectric Materials

Piezoelectric materials find applications in number of devices requiring inter-conversion of mechanical and electrical energy.  These devices include different types of sensors, actuators and energy harvesting devices. A number of lead-based perovskite compositions (PZT, PMN-PT, PZN-PT etc.) have dominated the field in last few decades owing to their giant piezoresponse and convenient application relevant tunability. With increasing environmental concerns, in the last one decade, focus has been shifted towards developing a better understanding of lead-free piezoelectric compositions in order to achieve an improved application relevant performance.  Sodium potassium niobate (KxNa1-xNbO3, abbreviated as KNN) is one of the most interesting candidates in the class of lead-free piezoelectrics. Absence of any poisonous element makes it unique among all the other lead-free candidates having presence of bismuth. Curie temperature of 400"C, even higher than that of PZT is another advantage from the point of view of device applications.

Present work focuses on the development of fundamental understanding of the crystallographic nature, domain structure and domain dynamics of KNN. Since compositions close to x = 0.5 are of primary interest because of their superior piezoelectric activity among other compositions (0 < x < 1), crystallographic and domain structure studies are focused on this region of the phase diagram. KNN random ceramic, textured ceramic and single crystals were synthesized, which in complement to each other help in understanding the behavior of KNN.

K0.5Na0.5NbO3 single crystals grown by the flux method were characterized for their ferroelectric and piezoelectric behavior and dynamical scaling analysis was performed to reveal the origin of their moderate piezoelectric performance. Optical birefringence technique used to reveal the macro level crystallographic nature of x = 0.4, 0.5 and 0.6 crystals suggested them to have monoclinic Mc, monoclinic MA/B and orthorhombic structures respectively. Contrary to that, pair distribution function analysis performed on same composition crystals implies them to belonging to monoclinic Mc structure at local scale. Linear birefringence and piezoresponse force microscopy (PFM) were used to reveal the domain structure at macro and micros scales respectively.

A noble sintering technique was developed to achieve > 99% density for KNN ceramics. These high density ceramics were characterized for their dielectric, ferroelectric and piezoelectric properties. A significant improvement in different piezoelectric coefficients of these ceramics validates the advantages of this sintering technique. Also lower defect levels in these high density ceramics lead to the superior ferroelectric fatigue behavior as well. To understand the role of seed crystals in switching behavior of textured ceramic, highly textured KNN ceramics (Lotgering factor ~ 88 %) were synthesized using TGG method. A sintering technique similar to one employed for random ceramics, was used to sinter textured KNN ceramics as well. Piezoresponse force microscopy (PFM) study suggested these textured ceramics to have about 6¼m domains as compared to 2¼m domain size for random ceramics.  Local switching behavior studied using switching spectroscopy (SS-PFM) revealed about two and half time improvement of local piezoresponse as compared to random counterpart. / Ph. D.

Identiferoai:union.ndltd.org:VTETD/oai:vtechworks.lib.vt.edu:10919/50959
Date10 June 2013
CreatorsGupta, Shashaank
ContributorsMaterials Science and Engineering, Priya, Shashank, Viehland, Dwight D., Heremans, Jean J., Suchicital, Carlos T. A.
PublisherVirginia Tech
Source SetsVirginia Tech Theses and Dissertation
Detected LanguageEnglish
TypeDissertation
FormatETD, application/pdf, application/pdf
RightsIn Copyright, http://rightsstatements.org/vocab/InC/1.0/

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