Lead-free ferroelectric glass-ceramics and composites

  • Abdulkarim Khalf

Student thesis: Phd


Glass-ceramic composites and nanocrystalline glass-ceramics containing barium titanate (BT) or potassium sodium niobate (KNN) ferroelectric phases have been studied, with particular regard to their use as dielectric energy storage materials. Barium borosilicate glass (BBS) was used as a sintering aid for BT and KNN, producing glass-ceramic composites. The temperatures required to achieve densification were reduced from 1400 to 1200 °C for BCZT (Ca, Zr-doped BT) and 1170 to 1050 °C for KBN (Bi, Na, K, Zr-doped KNN) by the use of glass additives. An unexpected observation, found in both BCZT and KBN systems, was the heterogeneous dissolution of dopant elements into the glass, inducing additional anomalies in the relative permittivity-temperature relationships. For BCZT, the orthorhombic-tetragonal phase transformation temperature shifted upwards to ≈ 50 °C, which was attributed to modification of the Ca/Zr ratio by preferential dissolution of Ca into the glass phase. Similarly, for KBN the dopant elements appeared to be leached into the liquid phase during sintering, resulting in relative permittivity-temperature characteristics similar to those of pure KNN. A modified BBS glass having various KNN contents was prepared by the conventional melt-quenching method and then heat-treated to induce crystallisation, producing nanocrystalline glass-ceramics. It is shown that crystallisation of an intermediate barium niobate phase initiates at temperatures in the region of 650 °C; this is subsequently converted into perovskite KNN together with a second phase of Ba3Nb5O15 at temperatures from 700 to 800 °C. The final crystallite size was in the region of 30±7 nm. The highest dielectric energy storage density of 0.134(4) J cm-3 was obtained for a glass-modified BT ceramic at an electric field level of 5 kV mm-1. However, the energy storage efficiency of the BT-based ceramics was relatively poor and they displayed a general tendency for saturation, indicating potentially poor performance at higher field levels. On the other hand, the KNN-based ceramics exhibited slightly lower energy storage density values, up to 0.108(1) J cm-3, but with much improved linearity and energy storage efficiency. Therefore, the latter is considered to be more suitable as energy storage dielectrics. The BBS-KNN glass-ceramics yielded relatively low energy storage density, 0.035(2) J cm-3, but the dielectric linearity and storage efficiency were similar to or better than those of the KNN ceramics, indicating good potential for use as energy storage dielectrics at very high electric field levels as a result of their nanocrystalline microstructures.
Date of Award1 Aug 2018
Original languageEnglish
Awarding Institution
  • The University of Manchester
SupervisorRobert Cernik (Supervisor) & David Hall (Supervisor)


  • Lead free, glass-ceramics, XRD diffraction

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