Origin of Large Dielectric Constant with Large Remnant Polarization and Evidence of Magnetoelectric Coupling in Multiferroic La modified BiFeO3-PbTiO3 Solid Solution

The presence of superlattice reflections and detailed analyses of the powder neutron and x-ray diffraction data reveal that La rich (BF$_{0.50}$-LF$_{0.50}$)$_{0.50}$-(PT)$_{0.50}$ (BF-LF-PT) has ferroelectric rhombohedral crystal structure with space group \textit{$R3c$} at ambient conditions. The temperature dependence of lattice parameters, tilt angle, calculated polarization $(P_{s})$, volume, and integrated intensity of superlattice and magnetic reflections show an anomaly around 170 K. Impedance spectroscopy, dielectric and ac conductivity measurements were performed in temperature range $473K \leq T \leq 573K$ to probe the origin of large remnant polarization and frequency dependent broad transitions with large dielectric constant near $T_c^{FE}$. Results of impedance spectroscopy measurements clearly show contributions of both grain and grain boundaries throughout the frequency range ($10^{3}$ Hz$\leq f\leq 10^{7}$ Hz). It could be concluded that the grain boundaries are more resistive and capacitive as compared to the grains, resulting in inhomogeneities in the sample causing broad frequency dependent dielectric anomalies. Enhancement in dielectric constant and remnant polarization values are possibly due to space charge polarization caused by piling of charges at the interface of grains and grain boundaries. The imaginary parts of dielectric constant ($\epsilon^{\prime\prime}$) Vs frequency data were fitted using Maxwell-Wagner model at $T_c^{FE}(\sim 523$K) and model fits very well with the data up to $10^{5}$ Hz. Magnetodielectric measurements prove that the sample starts exhibiting magnetoelectric coupling at $\sim 170$ K, which is also validated by neutron diffraction data.Comment: 20 pages, 10 figure

Mass transport and electrochemical properties of La2Mo2O9 as a fast ionic conductor

La2Mo2O9, as a new fast ionic conductor, has been investigated widely due to its high ionic conductivity which is comparable to those of the commercialized materials. However, little work has been reported on the oxygen transport and diffusion in this candidate electrolyte material. The main purpose of this project was to investigate oxide ion diffusion in La2Mo2O9 and also the factors which could affect oxygen transport properties. Oxygen isotope exchange followed by Secondary Ion Mass Spectrometry (SIMS) measurements were employed to obtain oxygen diffusion profiles. A correlation between oxygen ion transport and the electrochemical properties such as ionic conductivity was built upon the Nernst Einstein equation relating the diffusivity to electrical conductivity. In-situ neutron diffraction and AC impedance measurements were designed and conducted to investigate the correlation between crystal structure and oxygen transport in the bulk materials. Other techniques, such as synthesis, microstructure studies, and thermal analysis were also adopted to study the electrochemical properties of La2Mo2O9. The results of the study on the effects of microstructure on oxygen diffusion in La2Mo2O9 revealed that the grain boundary component played a significant role in electrochemical performance, although the grain size seemed to have little influence on oxygen transport. The oxygen isotope exchange in 18O2 was successfully carried out by introducing a silver coating on the sample surface, which solved the main difficulty in applying oxygen isotope exchange on pure ionic conductors. The ionic conductivity obtained from the diffusion coefficients was consistent with the result from AC impedance spectroscopy. The number of mobile oxygen ions was estimated to be 5 per unit cell. There was a difference of oxygen self diffusion coefficient when the isotope exchange was conducted in 18O2 and H2 18O. The activation energy of oxygen diffusion in humidified atmosphere was higher than that measured in dry atmosphere. It indicated that the humidified atmosphere had affected oxygen transport in the material. The studies on hydroxyl incorporation and transport explained the decreased oxygen diffusion coefficients in wet atmosphere and also suggested proton conductivity in La2Mo2O9, which leads to further investigation on applications of La2Mo2O9 as a proton conductor. In-situ neutron diffraction and AC impedance measurement revealed a close relationship between crystal structure and ionic conductivity. The successful application of this technique provides a new method to simultaneously investigate crystal structure and electrical properties in electro-ceramics in the future

Disentangling instrumental broadening

A new procedure aiming at disentangling the instrumental profile broadening and the relevant X-ray powder diffraction (XRPD) profile shape is presented. The technique consists of three steps: denoising by means of wavelet transforms, background suppression by morphological functions and deblurring by a Lucy--Richardson damped deconvolution algorithm. Real XRPD intensity profiles of ceria samples are used to test the performances. Results show the robustness of the method and its capability of efficiently disentangling the instrumental broadening affecting the measurement of the intrinsic physical line profile. These features make the whole procedure an interesting and user-friendly tool for the pre-processing of XRPD data.Comment: 9 pages, 1 table, 1 figure; typos correcte

Mechanochemical synthesis and characterization of nanodimensional iron–cobalt spinel oxides

Iron–cobalt spinel oxide nanoparticles, CoxFe3−xO4 (x = 1, 2), of sizes below 10 nm have been prepared by combining chemical precipitation with high-energy ball milling. For comparison, their analogues obtained by thermal synthesis have also been studied. The phase composition and structural properties of the obtained materials have been investigated by means of X-ray diffraction, Mössbauer spectroscopy, infrared spectroscopy, temperature-programmed reduction and magnetization measurements. X-ray diffraction shows that after 1 h of mechanical treatment ferrites are formed. The measurement techniques employed indicate that longer milling induces an increase in crystal size while crystal defects decrease with treatment time. Magnetization and reduction properties are affected by the particles size, the iron/cobalt ratio and the synthesis conditions

Multiscale understanding of tricalcium silicate hydration reactions

Tricalcium silicate, the main constituent of Portland cement, hydrates to produce crystalline calcium hydroxide and calcium-silicate-hydrates (C-S-H) nanocrystalline gel. This hydration reaction is poorly understood at the nanoscale. The understanding of atomic arrangement in nanocrystalline phases is intrinsically complicated and this challenge is exacerbated by the presence of additional crystalline phase(s). Here, we use calorimetry and synchrotron X-ray powder diffraction to quantitatively follow tricalcium silicate hydration process: i) its dissolution, ii) portlandite crystallization and iii) C-S-H gel precipitation. Chiefly, synchrotron pair distribution function (PDF) allows to identify a defective clinotobermorite, Ca11Si9O28(OH)2.8.5H2O, as the nanocrystalline component of C-S-H. Furthermore, PDF analysis also indicates that C-S-H gel contains monolayer calcium hydroxide which is stretched as recently predicted by first principles calculations. These outcomes, plus additional laboratory characterization, yielded a multiscale picture for C-S-H nanocomposite gel which explains the observed densities and Ca/Si atomic ratios at the nano- and meso- scales.This work has been supported by Spanish MINECO through BIA2014-57658-C2-2-R, which is co-funded by FEDER, BIA2014-57658-C2-1-R and I3 (IEDI-2016-0079) grants. We also thank CELLS-ALBA (Barcelona, Spain) for providing synchrotron beam time at BL04-MSPD beamline

Thermophysical Phenomena in Metal Additive Manufacturing by Selective Laser Melting: Fundamentals, Modeling, Simulation and Experimentation

Among the many additive manufacturing (AM) processes for metallic materials, selective laser melting (SLM) is arguably the most versatile in terms of its potential to realize complex geometries along with tailored microstructure. However, the complexity of the SLM process, and the need for predictive relation of powder and process parameters to the part properties, demands further development of computational and experimental methods. This review addresses the fundamental physical phenomena of SLM, with a special emphasis on the associated thermal behavior. Simulation and experimental methods are discussed according to three primary categories. First, macroscopic approaches aim to answer questions at the component level and consider for example the determination of residual stresses or dimensional distortion effects prevalent in SLM. Second, mesoscopic approaches focus on the detection of defects such as excessive surface roughness, residual porosity or inclusions that occur at the mesoscopic length scale of individual powder particles. Third, microscopic approaches investigate the metallurgical microstructure evolution resulting from the high temperature gradients and extreme heating and cooling rates induced by the SLM process. Consideration of physical phenomena on all of these three length scales is mandatory to establish the understanding needed to realize high part quality in many applications, and to fully exploit the potential of SLM and related metal AM processes