Metastable monoclinic and orthorhombic phases and electric field induced irreversible phase transformation at room temperature in the lead-free classical ferroelectric BaTiO3

For decades it has been a well-known fact that among the few ferroelectric compounds in the perovskite family, namely, BaTiO3, KNbO3, PbTiO3, and Na1/2Bi1/2TiO3, the dielectric and piezoelectric properties of BaTiO3 are considerably higher than the others in polycrystalline form at room temperature. Further, similar to ferroelectric alloys exhibiting morphotropic phase boundary, single crystals of BaTiO3 exhibit anomalously large piezoelectric response when poled away from the direction of spontaneous polarization at room temperature. These anomalous features in BaTiO3 remained unexplained so far from the structural standpoint. In this work, we have used high-resolution synchrotron x-ray powder diffraction, atomic resolution aberration-corrected transmission electron microscopy, in conjunction with a powder poling technique, to reveal that at 300 K (i) the equilibrium state of BaTiO3 is characterized by coexistence of metastable monoclinic Pm and orthorhombic (Amm2) phases along with the tetragonal phase, and (ii) strong electric field switches the polarization direction from the 001] direction towards the 101] direction. These results suggest that BaTiO3 at room temperature is within an instability regime, and that this instability is the fundamental factor responsible for the anomalous dielectric and piezoelectric properties of BaTiO3 as compared to the other homologous ferroelectric perovskite compounds at room temperature. Pure BaTiO3 at room temperature is therefore more akin to lead-based ferroelectric alloys close to the morphotropic phase boundary where polarization rotation and field induced ferroelectric-ferroelectric phase transformations play a fundamental role in influencing the dielectric and piezoelectric behavior.

On the Room Temperature Ferromagnetic and Ferroelectric Properties of Pb(Fe1/2Nb1/2)O-3

We report the origin of room temperature (RT) ferromagnetic and ferroelectric properties of Pb(Fe1/2Nb1/2)O-3 (PFN) ceramic sample prepared by modified solid-state reaction synthesis by a single-step method, based on X-ray diffraction (XRD), neutron diffraction (ND), Mossbauer spectroscopy and electron paramagnetic resonance (EPR) spectroscopy results. Formation of single-phase monoclinic PFN ceramic with Cm space group was confirmed by XRD and ND at RT. The morphology studied by scanning electron microscopy (SEM) confirmed uniform microstructure of the sample with average grain size of similar to 2 mu m. The ND, Mossbauer spectroscopy, M-H loop and EPR studies were carried out to confirm the existence of weak ferromagnetism at RT. A clear opening of hysteresis (M-H) loop is evidenced as the existence of weak ferromagnetism at RT. EPR spectrum clearly shows the ferromagnetism through a good resonance signal. The symmetric EPR line shape with g = 1.9895 observed in PFN sample was identified to be due to Fe3+ ions. Mossbauer spectroscopy at RT shows superparamagnetic behaviour with presence of Fe in 3+ valence state. Ferroelectric P-E loops on PFN at RT confirm the existing ferroelectric ordering. Our observation is in agreement with literature, and it supports that the origin of ferromagnetism and ferroelectricity is isolated, i.e. from different regions in the sample. Our results do not support the multiferroic nature of PFN at RT.

Al based ultra-fine eutectic with high room temperature plasticity and elevated temperature strength

Developments of aluminum alloys that can retain strength at and above 250 degrees C present a significant challenge. In this paper we report an ultrafine scale Al-Fe-Ni eutectic alloy with less than 3.5 aa transition metals that exhibits room temperature ultimate tensile strength of similar to 400 MPa with a tensile ductility of 6-8%. The yield stress under compression at 300 degrees C was found to be 150 MPa. We attribute it to the refinement of the microstructure that is achieved by suction casting in copper mold. The characterization using scanning and transmission electron microscopy (SEM and TEM) reveals an unique composite structure that contains the Al-Al3Ni rod eutectic with spacing of similar to 90 nm enveloped by a lamellar eutectic of Al-Al9FeNi (similar to 140 nm). Observation of subsurface deformation under Vickers indentation using bonded interface technique reveals the presence of extensive shear banding during deformation that is responsible for the origin of ductility. The dislocation configuration in Al-Al3Ni eutectic colony indicates accommodation of plasticity in alpha-Al with dislocation accumulation at the alpha-Al/Al3Ni interface boundaries. In contrast the dislocation activities in the intermetallic lamellae are limited and contain set of planner dislocations across the plates. We present a detailed analysis of the fracture surface to rationalize the origin of the high strength and ductility in this class of potentially promising cast alloy. (C) 2015 Elsevier B.V. All rights reserved.

Effect of ultra-fast mixing in a microchannel due to a soft wall on the room temperature synthesis of gold nanoparticles

The room-temperature synthesis of mono-dispersed gold nanoparticles, by the reduction of chlorauric acid (HAuCl4) with tannic acid as the reducing and stabilizing agent, is carried out in a microchannel. The microchannel is fabricated with one soft wall, so that there is a spontaneous transition to turbulence, and thereby enhanced mixing, when the flow Reynolds number increases beyond a critical value. The objective of the study is to examine whether the nanoparticle size and polydispersity can be modified by enhancing the mixing in the microchannel device. The flow rates are varied in order to study nanoparticle formation both in laminar flow and in the chaotic flow after transition, and the molar ratio of the chlorauric acid to tannic acid is also varied to study the effect of molar ratio on nanoparticle size. The formation of gold nanoparticles is examined by UV-visual spectroscopy and the size distribution is determined using scanning electron microscopy. The synthesized nanoparticles size decreases from a parts per thousand yen6 nm to a parts per thousand currency sign4 nm when the molar ratio of chlorauric acid to tannic acid is increased from 1 to 20. It is found that there is no systematic variation of nanoparticle size with flow velocity, and the nanoparticle size is not altered when the flow changes from laminar to turbulent. However, the standard deviation of the size distribution decreases by about 30% after transition, indicating that the enhanced mixing results in uniformity of particle size.

Origin of room temperature weak-ferromagnetism in antiferromagnetic Pb(Fe2/3W1/3)O-3 ceramic

We report the origin of room temperature weak ferromagnetic behavior of polycrystalline Pb(Fe2/3W1/3)O-3 (PFW) powder. The structure and magnetic properties of the ceramic powder prepared by a Columbite method were characterized by X-ray and neutron diffraction, Mossbauer spectroscopy and magnetization measurements. Rietveld analysis of diffraction data confirm the formation of single phase PFW, without traces of any parasitic pyrochlore phase. PFW was found to crystallize in the cubic structure at room temperature. The Rietveld refinement of neutron diffraction data measured at room temperature confirmed the G-type antiferromagnetic structure of PFW in our sample. However, along with the antiferromagnetic (AFM) ordering of the Fe spins, we have observed the existence of weak ferromagnetism at room temperature through: (i) a clear opening of hysteresis (M-H) loop, (ii) bifurcation of the field cooled and zero-field cooled susceptibility; supported by Mossbauer spectroscopy results. The P-E loop measurements showed a non-linear slim hysteresis loop at room temperature due to the electronic conduction through the local inhomogeneities in the PFW crystallites and the inter-particle regions. By corroborating all the magnetic measurements, especially the spin glass nature of the sample, with the conduction behavior of the sample, we report here that the observed ferromagnetism originates at these local inhomogeneous regions in the sample, where the Fe-spins are not perfectly aligned antiferromagnetically due to the compositional disordering. (C) 2015 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Organic alloys of room temperature liquids thiophenol and selenophenol

The first examples of organic alloys of two room temperature liquids, obtained and characterized via in situ cryo-crystallography, are presented. Thiophenol and selenophenol, which exhibit isostructurality and similar modes of S center dot center dot center dot S and Se center dot center dot center dot Se homo-chalcogen interactions along with weak and rare S-H center dot center dot center dot S and Se-H center dot center dot center dot Se hydrogen bonds, are shown to form solid solutions exhibiting Veggard's law-like trends.

Mg/BN nanocomposites: Nano-BN addition for enhanced room temperature tensile and compressive response

The present study elucidates the effects of nanoscale boron nitride particles addition on the microstructural and mechanical characteristics of monolithic magnesium. Novel light-weight Mg nanocomposites containing 0.3, 0.6 and 1.2vol% nano-size boron nitride particulates were synthesized using the disintegrated melt deposition method followed by hot extrusion. Microstructural characterization of developed Mg/x-boron nitride composites revealed significant grain refinement due to the uniform distribution of nano-boron nitride particulates. Texture analysis of selected Mg-1.2 boron nitride nanocomposite showed an increase in the intensity of fiber texture alongside enhanced localized recrystallization when compared to monolithic Mg. Mechanical properties evaluation under indentation, tension and compression loading indicated superior response of Mg/x-boron nitride composites in comparison to pure Mg. The uniform distribution of nanoscale boron nitride particles and the modified crystallographic texture achieved due to the nano-boron nitride addition attributes to the superior mechanical characteristics of Mg/boron nitride nanocomposites.

Room temperature ferromagnetism and white light emissive CdS:Cr nanoparticles synthesized by chemical co-precipitation method

Undoped and Cr (3% and 5%) doped CdS nanoparticles were synthesized by chemical co-precipitation method. The synthesized nanocrystalline particles are characterized by energy dispersive X-ray analysis (EDAX), scanning electron microscope (SEM), X-ray Diffraction (XRD), transmission electron microscopy (TEM), diffuse reflectance spectroscopy (DRS), photoluminescence (PL), Electron paramagnetic resonance (EPR), vibrating sample magnetometer (VSM) and Raman spectroscopy. XRD studies indicate that Cr doping in host CdS result a structural change from Cubic phase to mixed (cubic + hexagonal) phase. Due to quantum confinement effect, widening of the band gap is observed for undoped and Cr doped CdS nanoparticles compared to bulk CdS. The average particle size calculated from band gap values is in good agreement with the TEM study calculation and it is around 4-5 nm. A strong violet emission band consisting of two emission peaks is observed for undoped CdS nanoparticles, whereas for CdS:Cr nanoparticles, a broad emission band ranging from 420 nm to 730 nm with a maximum at similar to 587 nm is observed. The broad emission band is due to the overlapped emissions from variety of defects. EPR spectra of CdS:Cr samples reveal resonance signal at g = 2.143 corresponding to interacting Cr3+ ions. VSM studies indicate that the diamagnetic CdS nanoparticles are transform to ferromagnetic for 3% Cr3+ doping and the ferromagnetic nature is diminished with increasing the doping concentration to 5%. (C) 2015 Elsevier B.V. All rights reserved.

Percolative switching in transition metal dichalcogenide field-effect transistors at room temperature

We have addressed the microscopic transport mechanism at the switching or `on-off' transition in transition metal dichalcogenide (TMDC) field-effect transistors (FETs), which has been a controversial topic in TMDC electronics, especially at room temperature. With simultaneous measurement of channel conductivity and its slow time-dependent fluctuation (or noise) in ultrathin WSe2 and MoS2 FETs on insulating SiO2 substrates where noise arises from McWhorter-type carrier number fluctuations, we establish that the switching in conventional backgated TMDC FETs is a classical percolation transition in a medium of inhomogeneous carrier density distribution. From the experimentally observed exponents in the scaling of noise magnitude with conductivity, we observe unambiguous signatures of percolation in a random resistor network, particularly, in WSe2 FETs close to switching, which crosses over to continuum percolation at a higher doping level. We demonstrate a powerful experimental probe to the microscopic nature of near-threshold electrical transport in TMDC FETs, irrespective of the material detail, device geometry, or carrier mobility, which can be extended to other classes of 2D material-based devices as well.