Structural studies of novel bismuth containing piezoelectric ceramics

Doctoral thesis English OPEN
Datta, Kaustuv
  • Subject: QC

Perovskite-based materials are in the focus of research not only because of their excellent\ud physical properties, but also because their relatively simple structure facilitates\ud the understanding of structure-property relationships, which is crucial for developing\ud novel materials with improved qualities. Recent research in the field of ferroelectric\ud and piezoelectric materials is concerned with the development of eco-friendly lead-free\ud materials. To achieve this goal, it is important to understand the fundamental correlation\ud between the ‘Structure’ and the ‘Property’. In this work, the primary focus has\ud been to elucidate the structural changes occurring as a function of doping in three different\ud systems: (1) BiScO3-PbTiO3 (BS-PT), a recently developed system which has\ud already attracted much interest because of its superior physical properties near the morphotropic\ud phase boundary (MPB); (2) BiScO3-BaTiO3 (BS-BT), which can be considered\ud as a lead-free analogue of the BS-PT family and lastly, (3) Na0.5Bi0.5TiO3-BaTiO3\ud (NBT-BT), which is a well-known lead-free material at the NBT-rich side of the phase\ud diagram.\ud Powder samples with a range of compositions for each system were prepared following\ud the solid-state synthesis route and were investigated utilizing both neutron and\ud x-ray powder diffraction and dielectric measurements. Detailed crystallographic information\ud was obtained by Rietveld refinement against the neutron powder diffraction\ud data. Structural phase transitions as a function of temperature were determined by nonambient\ud x-ray powder diffraction and compared with the physical properties of the ceramics\ud using high-temperature dielectric measurements. The significant outcomes are:\ud 1. The best model to represent the so-called MPB of xBS-(1-x)PT system is found to\ud be a mixture of a tetragonal and a monoclinic phases from the powder diffraction\ud data. The structure beyond the MPB compositions is in better agreement for a\ud single monoclinic model with the space group Cm than the accepted space group\ud R3m. By contrast, single crystals with compositions around the MPB provide\ud evidence for a model consisting of two primitive monoclinic cells.\ud 2. The lead-free BS-BT system exhibits an extended phase boundary between tetragonal\ud and pseudocubic phases, which can be modelled by a combination of tetragonal\ud and rhombohedral phases. The incorporation of BS into BT also results in\ud the suppression of the two low-temperature phase transitions of BT.\ud 3. Samples with new compositions synthesized in the xNBT-(1-x)BT system demonstrate\ud a rare enhancement in the tetragonality of the unit cell and an increase in\ud the Curie temperature for compositions where x <= 0.40.
  • References (50)
    50 references, page 1 of 5

    Chapter 1 Introduction 1 1.1 Piezoelectricity and crystal symmetry . . . . . . . . . . . . . . . . . . 1 1.2 An introduction to the Perovskite structure . . . . . . . . . . . . . . . . 4 1.2.1 Prototype cubic perovskite . . . . . . . . . . . . . . . . . . . . 4 1.2.2 Structural variations in perovskite . . . . . . . . . . . . . . . . 6 1.3 Current status of piezoeletric materials . . . . . . . . . . . . . . . . . . 8 1.3.1 Open issues . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8 1.3.2 Lead-based materials and Morphotropic Phase boundary (MPB) 10 1.3.3 Reduced-lead materials . . . . . . . . . . . . . . . . . . . . . . 13 1.3.4 Lead-free materials . . . . . . . . . . . . . . . . . . . . . . . . 14 1.4 Scope of this thesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21 Chapter 2 Background to Experimental Methods 25 2.1 Preparation of powder samples . . . . . . . . . . . . . . . . . . . . . . 25 2.2 X-ray and neutron powder di raction . . . . . . . . . . . . . . . . . . 27 2.2.1 X-ray powder di raction . . . . . . . . . . . . . . . . . . . . . 27

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