Ajay Kumar Kalyani

Orthorhombic-tetragonal phase coexistence and enhanced piezo-response at room temperature in Zr, Sn, and Hf modified BaTiO3

The effect of Zr, Hf, and Sn in BaTiO3 has been investigated at close composition intervals in the dilute concentration limit. Detailed structural analysis by x-ray and neutron powder diffraction revealed that merely 2mol. % of Zr, Sn, and Hf stabilizes a coexistence of orthorhombic (Amm2) and tetragonal (P4mm) phases at room temperature. As a consequence, all the three systems show substantial enhancement in the longitudinal piezoelectric coefficient (d(33)), with Sn modification exhibiting the highest value similar to 425 pC/N

Polymorphic phase boundaries and enhanced piezoelectric response in extended composition range in the lead free ferroelectric BaTi1−xZrxO3

Neutron powder diffraction study of Ba(Ti1−xZrx)O3 at close composition intervals has revealed coexistence of ferroelectric phases: orthorhombic (Amm2) + tetragonal (P4mm) for 0.02 ≤ x ≤0.05 and rhombohedral (R3m) + orthorhombic (Amm2) for 0.07 ≤ x < 0.09. These compositions exhibit relatively enhanced piezoelectric properties as compared to their single phase counterparts outside this composition region, confirming the polymorphic phase boundary nature of the phase coexistence regions.

Ferroelectric instabilities and enhanced piezoelectric response in Ce modified BaTiO3 lead-free ceramics

The crystal structure, ferroelectric, and piezoelectric behaviors of the Ba(Ti1−xCex)O3 solid solution have been investigated at close composition intervals in the dilute concentration regime. Ce concentration as low as 2 mol. % induces tetragonal-orthorhombic instability and coexistence of the phases, leading to enhanced high-field strain and direct piezoelectric response. Detailed structural analysis revealed tetragonal + orthorhombic phase coexistence for x = 0.02, orthorhombic for 0.03 ≤ x ≤ 0.05, and orthorhombic + rhombohedral for 0.06 ≤ x ≤ 0.08. The results suggest that Ce-modified BaTiO3 is a potential lead-free piezoelectric material.

Competing A-site and B-site driven ferroelectric instabilities in the (1−x)PbTiO3-(x)BiAlO3 system

The system (1-x)PbTiO3-(x)BiAlO3 has been investigated with regard to its solid solubility, crystal structure, microstructure, and ferroelectric transition. The unit cell volume and the tetragonality exhibit anomalous behavior near x=0.10. The Curie point (T-C) of PbTiO3 was however found to be nearly unchanged. The study seems to suggest that the decrease in the stability of the ferroelectric state due to dilution of the Ti-sublattice by smaller sized Al+3 ions is compensated by the increase in the ferroelectric stability by the Bi+3 ions.

Anomalous piezoelectric response due to stabilization of two ferroelectric phases in Zr-modified BaTiO3

The lead-free Ba(Ti1-xZrx)O3 ceramic has shown enhanced piezo-response (d33) in a narrow composition interval (0.01 ≤ x ≤ 0.03) exhibiting the coexistence of two ferroelectric phases. The system presents two electric-field-dependent-property regimes: (i) a low field regime (E < 1.7 kV mm(-1)) where d33 is nearly independent of the poling field, and (ii) E > 1.7 kV mm(-1) for which d33 drops sharply. X-ray diffraction studies revealed that the later phenomenon is related to field driven irreversible structural transformation, which tends to drive the system away from an equilibrium two phase state to a nearly single phase metastable state.

Zirconia doped barium titanate induced electroactive β polymorph in PVDF-HFP: high energy density and dielectric properties

Zirconium-doped barium titanate (BZT-08, Ba(Ti0.92 Zr0.08)O3) particles were synthesized and PVDF-HFP-based composites were prepared by melt mixing to design materials with tunable dielectric and ferroelectric properties. Composites of PVDF-HFP and barium titanate (BT) particles were also prepared to realize the exceptional properties associated with the BZT-08-like stabilization of two ferroelectric phases, i.e. tetragonal and orthorhombic at room temperature. To facilitate the uniform dispersion and interfacial adhesion with the matrix, the particles were modified with (3-aminopropyl) triethoxysilane. The dependence of the dielectric and ferroelectric properties of the as-prepared composites were systematically investigated in this study with respect to a wide range of frequencies. The composites with BZT-08 exhibited the significantly high dielectric permittivity of ca. 26 (at 100 Hz) and a high energy density (2.7 J cm−3 measured on 100 μm thick film) at room temperature with respect to the control PVDF-HFP and PVDF-HFP/BT composites. Interestingly, the BZT-08 particles facilitated the electroactive β polymorph in the PVDF-HFP and enhanced polarization in the composites, leading to improved ferroelectric properties in the composites.

Tendency to promote ferroelectric distortion in Pr-modified PbTiO3

Structural, microstructural, and dielectric studies have been carried out on Pr-modified PbTiO3. A comparative analysis with La-modified PbTiO3 suggests that for chemical modification by same amount, the Pr-modified system has larger tetragonal strain and Curie point. No clear feature of relaxor ferroelectric state is observed for Pr concentration as high as x=0.35, suggesting that Pr modification is less effective, as compared to La-modification, in inducing a relaxor ferroelectric state. Results suggest that inspite of increased chemical disorder, Pr modification partly tends to restore the ferroelectric distortion of the lattice through partial occupancy of the Pr4+ ions on the Ti4+ sites.