Phase boundary at x=0.03 and its anomalous influence on the structure and properties in the lead-free piezoelectric (1-x)Na1/2Bi1/2TiO3-(x)BaTiO3

The complexity associated with local structures continues to pose challenges with regard to the understanding of the structure-property relationship in Na1/2Bi1/2TiO3-based lead-free piezoceramics. (1-x)Na1/2Bi1/2TiO3-(x)BaTiO3 is an extensively studied system because of its interesting piezoelectric properties. Recently, a room temperature phase boundary was reported at x = 0.03 in this system Ma et al., Adv. Funct. Mater. 23, 5261 (2013)]. In the present work we have examined this subtle phase boundary using x-ray diffraction, neutron diffraction, dielectric measurements as a function of composition (x < 0.06), temperature, and electric field. Our results show that this boundary separates an R3c + Cc-like structural state for x < 0.03 from an R3c+ cubiclike structural state for 0.03 <= x <= 0.05 in the unpoled specimens. This phase boundary is characterized by an anomalous reduction in the depolarization temperature, and a suppression of the tetragonal distortion of the high temperature P4bm phase. Our results also provide the clue to understand the pathway leading to the cubiclike structure of the critical composition x = 0.06, known for its highest piezoelectric response.

Relaxor ferroelectricity and electric-field-driven structural transformation in the giant lead-free piezoelectric (Ba,Ca)(Ti, Zr)O-3

There is great interest in lead-free (Ba0.85Ca0.15)(Ti0.90Zr0.10)O-3 (15/10BCTZ) because of its exceptionally large piezoelectric response Liu and Ren, Phys. Rev. Lett. 103, 257602 (2009)]. In this paper, we have analyzed the nature of: (i) crystallographic phase coexistence at room temperature, (ii) temperature-and field-induced phase transformation to throw light on the atomistic mechanisms associated with the large piezoelectric response of this system. A detailed temperature-dependent dielectric and lattice thermal expansion study proved that the system exhibits a weak dielectric relaxation, characteristic of a relaxor ferroelectric material on the verge of exhibiting a normal ferroelectric-paraelectric transformation. Careful structural analysis revealed that a ferroelectric state at room temperature is composed of three phase coexistences, tetragonal (P4mm)+ orthorhombic (Amm2) + rhombohedral (R3m). We also demonstrate that the giant piezoresponse is associated with a significant fraction of the tetragonal phase transforming to rhombohedral. It is argued that the polar nanoregions associated with relaxor ferroelectricity amplify the piezoresponse by providing an additional degree of intrinsic structural inhomogeneity to the system.

Twinning induced enhancement of fracture toughness in ultrafine grained Hydroxyapatite-Calcium Titanate composites

Despite being highly bioactive and biocompatible, the limitations of monolithic hydroxyapatite (HA) include extremely low fracture toughness, poor electrical conductivity. While addressing these issues, the present study demonstrates how CaTiO3 (CT) addition to HA can be utilized to obtain a combination of long crack fracture toughness (1.7 MPa m(1/2) SEVNB technique) and flexural strength of 98-155 MPa (3-point bending) and a moderate tensile strength (diametral compression) of 17-36 MPa. The enhancement in fracture resistance in spark plasma sintered HA-CT composites has been explained in reference to the observed twin morphology. TEM reveals the presence of twins in CT grains due to 1800 rotation about 101]. The measured properties along with our earlier reports on biocompatibility and electrical properties make HA-CT suitable for bone tissue engineering applications. When compared with other competing HA-based biocomposites, HA-CT composites are found to have a better combination of properties useful for medium load bearing implant applications. (C) 2015 Elsevier Ltd. All rights reserved.

Electric field and temperature dependence of the local structural disorder in the lead-free ferroelectric Na0.5Bi0.5TiO3: An EXAFS study

The complex nature of the structural disorder in the lead-free ferroelectric Na1/2Bi1/2TiO3 has a profound impact on the perceived global structure and polar properties. In this paper, we have investigated the effect of electric field and temperature on the local structure around theBi and Ti atoms using extended x-ray absorption fine structure. Detailed analysis revealed that poling brings about a noticeable change in the bond distances associated with the Bi-coordination sphere, whereas the Ti coordination remains unaffected. We also observed discontinuity in the Bi-O bond lengths across the depolarization temperature of the poled specimen. These results establish that the disappearance of the monoclinic-like (Cc) global distortion, along with the drastic suppression of the short-ranged in-phase octahedral tilt after poling B. N. Rao et al., Phys. Rev. B 88, 224103 (2013)] is a result of the readjustment of theA-O bonds by the electric field, so as to be in conformity with the rhombohedral R3c structure.

Mutations in the nucleotide binding and hydrolysis domains of Helicobacter pylori MutS2 lead to altered biochemical activities and inactivation of its in vivo function

Background: Helicobacter pylori MutS2 (HpMutS2), an inhibitor of recombination during transformation is a non-specific nuclease with two catalytic sites, both of which are essential for its anti-recombinase activity. Although HpMutS2 belongs to a highly conserved family of ABC transporter ATPases, the role of its ATP binding and hydrolysis activities remains elusive. Results: To explore the putative role of ATP binding and hydrolysis activities of HpMutS2 we specifically generated point mutations in the nucleotide-binding Walker-A (HpMutS2-G338R) and hydrolysis Walker-B (HpMutS2-E413A) domains of the protein. Compared to wild-type protein, HpMutS2-G338R exhibited similar to 2.5-fold lower affinity for both ATP and ADP while ATP hydrolysis was reduced by similar to 3-fold. Nucleotide binding efficiencies of HpMutS2-E413A were not significantly altered; however the ATP hydrolysis was reduced by similar to 10-fold. Although mutations in the Walker-A and Walker-B motifs of HpMutS2 only partially reduced its ability to bind and hydrolyze ATP, we demonstrate that these mutants not only exhibited alterations in the conformation, DNA binding and nuclease activities of the protein but failed to complement the hyper-recombinant phenotype displayed by mutS2-disrupted strain of H. pylori. In addition, we show that the nucleotide cofactor modulates the conformation, DNA binding and nuclease activities of HpMutS2. Conclusions: These data describe a strong crosstalk between the ATPase, DNA binding, and nuclease activities of HpMutS2. Furthermore these data show that both, ATP binding and hydrolysis activities of HpMutS2 are essential for the in vivo anti-recombinase function of the protein.

Dielectric investigation of high-k yttrium copper titanate thin films

We report on the first dielectric investigation of high-k yttrium copper titanate thin films, which were demonstrated to be very promising for nanoelectronics applications. The dielectric constant of these films is found to vary from 100 down to 24 (at 100 kHz) as a function of deposition conditions, namely oxygen pressure and film thickness. The physical origin of such variation was investigated in the framework of universal dielectric response and Cole-Cole relations and by means of voltage dependence studies of the dielectric constant. Surface-related effects and charge hopping polarization processes, strictly dependent on the film microstructure, are suggested to be mainly responsible for the observed dielectric response. In particular, the bulky behaviour of thick films deposited at lower oxygen pressure evolves towards a more complex and electrically heterogeneous structure when either the thickness decreases down to 50 nm or the films are grown under high oxygen pressure.

Dielectric investigation of high-k yttrium copper titanate thin films

We report on the first dielectric investigation of high-k yttrium copper titanate thin films, which were demonstrated to be very promising for nanoelectronics applications. The dielectric constant of these films is found to vary from 100 down to 24 (at 100 kHz) as a function of deposition conditions, namely oxygen pressure and film thickness. The physical origin of such variation was investigated in the framework of universal dielectric response and Cole-Cole relations and by means of voltage dependence studies of the dielectric constant. Surface-related effects and charge hopping polarization processes, strictly dependent on the film microstructure, are suggested to be mainly responsible for the observed dielectric response. In particular, the bulky behaviour of thick films deposited at lower oxygen pressure evolves towards a more complex and electrically heterogeneous structure when either the thickness decreases down to 50 nm or the films are grown under high oxygen pressure.

Structural, Optical, and Piezoelectric Response of Lead-Free Ba0.95Mg0.05Zr0.1Ti0.9O3 Nanocrystalline Powder

Nanocrystalline powders of Ba1-xMgxZr0.1Ti0.9O3 (x = 0.025-0.1) were synthesized via citrate assisted sol-gel method. Interestingly, the one with x = 0.05 in the system Ba1-xMgxZr0.1Ti0.9O3 exhibited fairly good piezoelectric response aside from the other physical properties. The phase and structural confirmation of synthesized powder was established by X-ray powder diffraction (XRD) and Raman Spectroscopic techniques. Two distinct Raman bands i.e., 303 and 723 cm(-1) characteristic of tetragonal phase were observed. Thermogravimetric analysis (TGA) was performed to evaluate the phase decomposition of the as-synthesized Ba0.95Mg0.05Zr0.1Ti0.9O3 sample as a function of temperature. The average crystallite size associated with Ba0.95Mg0.05Zr0.1Ti0.9O3 was calculated using Scherrer formula based on the XRD data and was found to be 25 nm. However, Scanning and Transmission Electron Microscopy studies revealed the average crystallite size to be in the range of 30-40 nm, respectively. Kubelka-Munk function was employed to determine the optical band gap of these nanocrystallites. A piezoelectric response of 26 pm/V was observed for Ba0.95Mg0.05Zr0.1Ti0.9O3 nanocrystal by Piezoresponse Force Microscopy (PFM) technique. Photoluminescence (PL) study carried out on these nanocrystals exhibited a blue emission (470 nm) at room temperature.

Long-period modulated structure and electric-field-induced structural transformation in Na0.5Bi0.5TiO3-based lead-free piezoelectrics

Na0.5Bi0.5TiO3- based lead-free piezoelectrics exhibiting giant piezostrain are technologically interesting materials for actuator applications. The lack of clarity with regard to the structure of the nonpolar phase of this system has hindered the understanding of the structural mechanism associated with the giant piezostrain and other related phenomena. In this paper, we have investigated the structure and field-induced phase transformation behavior of a model system (0.94 - x) Na0.5Bi0.5TiO3-0.06BaTiO(3)-xK(0.5)Na(0.5)NbO(3) (0.0 <= x <= 0.025). A detailed structural analysis using neutron powder diffraction revealed that the nonpolar phase is neither cubic nor a mixture of rhombohedral (R3c) and tetragonal (P4bm) phases as commonly reported in literature but exhibits a long-period modulated structure, which is most probably of the type root 2 x root 2 x n with n = 16. Our results suggest that the giant piezoelectric strain is associated with a field-induced phase transformation of the long-period modulated structure to rhombohedral R3c structure above a critical field. We also demonstrate that the giant piezostrain is lost if the system retains a fraction of the field-induced R3c phase. A possible correlation among depolarization temperature, giant piezostrain, and its electrical fatigue behavior has also been indicated.