Dielectric,ferroelectric, and piezoelectric properties of lead-free Ba0.95Ca0.05Ti1-xZrxO3 ceramics

Abstract

Ba_0.95Ca_0.05Ti_1-xZr_xO₃ (BCTZO) ceramics were prepared by a solid state reaction method. The samples were characterized by X-ray diffraction (XRD), Scanning electron microscopy (SEM) and X-ray absorption near edge structure (XANES). The ceramics exhibit a pure perovskite structure. The average grain size gradually decreases with increasing Zr concentration. XANES results indicate that the intensities of pre-edge peaks dropped with increasing Zr concentration. The BCTZO ceramic of x?=?0.05 has the optimum electrical properties with the maximum dielectric constant (ε'_m), remanent polarization (2P_r), coercive electric field (2E_c) and piezoelectric charge constant (d₃₃) of 7,244, 12.54 (μC/cm²), 5.29 (kV/cm) and 288 (pC/N), respectively.     

Phase-change optical recording: Past, present, future

We discuss specific features of Te-based compounds that made them the best materials for the phase-change data storage. It is demonstrated that the phase-change recording is due to a switch of Ge atoms between octahedral and tetrahedral symmetry positions within the Te face-centered cubic lattice. It is this nature of the transition that makes the Te-based media fast and stable. The driving force for this transition is also discussed. The chapter is concluded by introduction of a concept of the super-resolution near-field structure (super-RENS) disc that allows to reduce a bit size well below the diffraction limit and makes 100 GB/disc storage a reality.     

Synthesis of LiFePO4 with fine particle by co-precipitation method

LiFePO₄ is a potential candidate for the cathode material of the lithium secondary batteries. A co-precipitation method was adopted to prepare LiFePO₄ because it is simple and cheap. Nitrogen gas was needed to prevent oxidation of Fe²⁺ in the aqueous solution. The co-precipitated precursor shows the high reactivity with the reductive gas, and the single phase of LiFePO₄ is successfully synthesized with the aid of carbon under less reductive conditions. LiFePO₄ fine powder prepared by co-precipitation method shows high rate capability, impressive specific capacity and cycle property.     

Relating catalyst structure and composition to the water–gas shift activity of Cu–Zn-based mixed-oxide catalysts

In order to investigate the effect of cerium oxide on Cu–Zn-based mixed-oxide catalysts four catalyst samples were characterized by means of XRD, in situ XANES and thermogravimetric analysis. The activity of the catalyst samples was tested for the forward water–gas shift reaction. Cerium oxide was found to increase the crystallinity of the ZnO phase indicating a segregation of the Cu and ZnO phases. The TOF of the water–gas shift reaction based on chemisorption data was found to be independent of composition and preparation conditions of the four catalyst samples. In contrast, the catalyst stability depends on composition and preparation conditions. Cerium oxide impregnated before calcination of the hydrotalcite-based Cu–Zn precursors leads to a more stable water–gas shift catalyst.     

Analysis of XANES for identification of highly dispersed transition metal oxides on supports

XANES of vanadium and niobium oxide on silica or alumina have been analyzed quantitatively by a deconvolution technique. Based on the results for reference compounds, local structures of supported vanadium and niobium species were identified. The composition was estimated from difference spectra for the samples which consisted of two kinds of species.     

A new synthesis procedure for titanium-containing zeolites under strong alkaline conditions and the catalytic activity for partial oxidation and photocatalytic decomposition

A new synthesis procedure for titanium-containing aluminosilicate zeolites has been obtained using a clear colloidal dispersion (sol) which was prepared with titanium isopropoxide, water, hydrochloric acid and colloidal silica, Ludox. When NaY, KL, offretite, mordenite and ZSM-5 zeolites were crystallized from the sol following conventional hydrothermal crystallization procedures, all the aluminosilicate zeolites showed the same X-ray absorption fine structure at the Ti K edge indicating framework Ti. The zeolites showed remarkable catalytic activity for the partial oxidation of cyclohexene using H₂O₂ as an oxidant and the photocatalytic decomposition of trichloroethene using water.     

Adsorption mode of ethyl pyruvate on platinum: an in situ XANES study

The adsorption of ethyl pyruvate on Pt(111) has been studied by in situ XANES measurements in the presence and absence of hydrogen. Depending on the hydrogen and ethyl pyruvate pressure, the C and O K‐edge spectra exhibit distinctly different angular dependence. Without hydrogen ethyl pyruvate is oriented preferentially perpendicular to the surface, indicating bonding via the O lone pairs. In the presence of hydrogen the mean orientation is more tilted towards the surface. Likely, ethyl pyruvate also interacts with Pt via its π system under these conditions. The observed angle‐dependent shift of the energy of the π* and σ* resonances indicates the coexistence of differently adsorbed ethyl pyruvate species. The experimental findings demonstrate the importance of the in situ approach for unraveling the adsorption mode of ethyl pyruvate in the enantioselective hydrogenation over cinchona‐alkaloid‐modified Pt. This revised version was published online in July 2006 with corrections to the Cover Date.     

The use of X‐ray absorption spectroscopy for monitoring the thickness of antiwear films from ZDDP

X‐ray absorption near edge structure (XANES) spectroscopy at the P K‐edge was used to monitor ZDDP antiwear film thickness with rubbing time. Thermal immersion films of varying thickness were generated from the ZDDP and analysed using XANES spectroscopy and the particle induced X‐ray emission (PIXE) technique. P K‐edge XANES edge jumps and (1s → np) peak heights of the spectra were plotted against PIXE mass thickness values in order to establish calibration curves. Antiwear films were analysed using XANES spectroscopy, and average mass thicknesses were extrapolated from the calibration curves. A set of antiwear films formed in the presence of ZDDP and then further rubbed in base oil (no ZDDP) showed no significant decrease in film thickness. A set of antiwear films rubbed in the presence of ZDDP for various lengths of time showed an increase in film thickness, followed by thinning of the film. The decrease in film thickness is believed to be due to wear caused by the ZDDP solution decomposition products acting as an abrasive in the contact region. This revised version was published online in July 2006 with corrections to the Cover Date.     

Conversion of hydrogen/carbon dioxide into formic acid and methanol over Cu/CuCr2O4 catalyst

Cu/CuCr₂O₄ catalysts were prepared by impregnation method at various calcination temperatures (300, 400, and 500 °C) and then reduced in H₂ stream. The aggregated particles and decreasing surface area/pore volumes of the deactivated catalysts during HCOOH and CH₃OH formations were also observed. Particularly, the EXAFS data showed that first shells of Cu atoms transforms from Cu–O to Cu–Cu after catalytic reactions, their bond distances and coordination numbers are quite different, respectively. It revealed that metallic Cu atoms are one of the important active species over catalyst surface at different reaction temperatures having many unoccupied binding sites for HCOOH and CH₃OH formations. Additionally, the optimal calcination temperature for Cu/CuCr₂O₄ catalysts was demonstrated at 400 °C that attributed to its strongest acidity and basicity. The catalytic reactions in the duration of HCOOH and CH₃OH preparation were proposed that were composed of HCOOH formation, CH₃OH formation, and CH₃OH decomposition happening at CuCr₂O₄, Cu, and CuO active sites, respectively. The highest CO₂ conversion (14.6%), HCOOH selectivity/yield (87.8/12.8%), and TON/TOF values (4.19/0.84) were obtained at 140 °C and 30 bar in 5 h, respectively. Optimal rate constant (2.57 × 10^?2 min^?1) and activation energy (16.24 kJ mol^?1) of HCOOH formation were evaluated by pseudo first-order model and Arrhenius equation, respectively.     

Experimental methods in chemical engineering: X-ray absorption spectroscopy—XAS,XANES, EXAFS

Although X-ray absorption spectroscopy (XAS) was conceived in the early 20th century, it took 60 years after the advent of synchrotrons for researchers to exploit its tremendous potential. Counterintuitively, researchers are now developing bench type polychromatic X-ray sources that are less brilliant to measure catalyst stability and work with toxic substances. XAS measures the absorption spectra of electrons that X-rays eject from the tightly bound core electrons to the continuum. The spectrum from 10 to 150 eV (kinetic energy of the photoelectrons) above the chemical potential—binding energy of core electrons—identifies oxidation state and band occupancy (X-ray absorption near edge structure, XANES), while higher energies in the spectrum relate to local atomic structure like coordination number and distance, Debye-Waller factor, and inner potential correction (extended X-ray absorption fine structure, EXAFS). Combining XAS with complementary spectroscopic techniques like Raman, Fourier transform infrared (FTIR), X-ray photoelectron spectroscopy (XPS), and electron paramagnetic resonance (EPR) elucidates the nature of the chemical bonds at the catalyst surface to better understand reaction mechanisms and intermediates. Because synchrotrons continue to be the light source of choice for most researchers, the number of articles Web of Science indexes per year has grown from 1000 in 1991 to 1700 in 2020. Material scientists and physical chemists publish an order of magnitude articles more than chemical engineers. Based on a bibliometric analysis, the research comprises five clusters centred around: electronic and optical properties, oxidation and hydrogenation catalysis, complementary analytical techniques like FTIR, nanoparticles and electrocatalysis, and iron, metals, and complexes.