The adsorption of 1,10-phenanthroline (OP) onto some clays and oxides was studied as a function of concentration, pH, and time. The adsorption was found to be irreversible and the isotherms, except for silica gel, were hyperbolic and gave rise to plots similar to that of Langmuir. Kinetic and light scattering studies show that OP is adsorbed as a micellar unit composed on the average of 3.5 molecules/micelle. This fact explains the overestimation observed in the surface areas of some sorbents since no true monomolecular layer of OP is formed on the surfaces. The adsorption was also found to be pH dependent, attaining a maximum, independent of the sorbent, at about pH 6. This maximum was approximately at the same pH in which only the molecular form of OP began to be present. The partial desorption of OP as the pH increased beyond 6 is possibly associated with the aggregation of micelles on the surfaces.

The aim of this study was to compare the redox properties of oxides and smectite structural Fe (FeStr). Structural Fe in smectite often accounts for about half of the Fe pool in soils and sediments, and is naturally reduced by indigenous bacteria. This reaction is, however, seldom taken into account in environmental studies. The equation for the oxidation-reduction of FeStr and its application to the calculation of the standard electrode potential of FeStr, E0, are discussed on the basis of literature review. The resulting redox properties were used in a new analysis of previously reported field monitoring data. This agreed well with experimental observations that remained unexplained, and showed that if equilibrium conditions prevail, the FeStr pool in soils will reduce prior to the Fe in oxides. The FeStr pool is, therefore, likely to play a major role in controlling the bio-geochemistry of temporarily water-logged soils, and this reaction should be taken into account in further studies.

Polycrystalline Ba0.8Sr0.2Ti0.6Zr0.3Mn0.1O3 was synthesized by solid-state reaction at 1600°C. The single phase formation of the compound without any impurities was confirmed by the X-ray diffraction technique. The prepared compound crystallized to a cubic structure with a space group of Pm-3m and the refined lattice parameters were a = b = c = 4.0253 Ǻ, α = β = γ = 90°. Rietveld refinement was carried for the powder XRD data using GSAS software and the experimental data peaks were indexed by Powder X software.

Nanocrystalline oxides are mainly responsible for Ni-base oxide dispersion strengthened (ODS) superalloys excellent thermo-mechanical properties. To establish the microstructural correlations between the metallic matrix and various oxide dispersoids, we report here the atomic-scale structure and chemistry of the complex nano-oxide dispersoids. Ultrahigh-resolution Cs-aberration-corrected scanning transmission electron microscopy (STEM) based techniques have been used to resolve nano-dispersoids in the Alloy 617 ODS. These nano-oxides, interestingly, possess a variety of high-angle annular dark-field (HAADF) contrasts, that is, bright, dark, and bi-phases. Both the light and heavy atoms have been found to be present in Y–Al–O complex-oxide nanostructures in varying quantities and forming a characteristic interface with the metallic matrix. In overcoming the limitation of conventional STEM-HAADF imaging, the integrated differential phase-contrast imaging technique was employed to investigate the oxygen atoms along with other elements in the dispersoids and its interface with the matrix. The most intriguing aspect of the study is the discovery of a few atoms thick Al2O3 interlayer (shell) around a monoclinic Y–Al–O core in the Ni-matrix. On the other hand, when the dispersoid is a hexagonal type Y–Al–O complex, the interface energy is already low, maintaining a semi-coherent interface and it was devoid of a shell.

The search space for new thermoelectric oxides has been limited to the alloys of a few known systems, such as ZnO, SrTiO3, and CaMnO3. Notwithstanding the high power factor, their high thermal conductivity is a roadblock in achieving higher efficiency. In this paper, we apply machine learning (ML) models for discovering novel transition metal oxides with low lattice thermal conductivity ($ {k}_L $). A two-step process is proposed to address the problem of small datasets frequently encountered in material informatics. First, a gradient-boosted tree classifier is learnt to categorize unknown compounds into three categories of $ {k}_L $: low, medium, and high. In the second step, we fit regression models on the targeted class (i.e., low $ {k}_L $) to estimate $ {k}_L $ with an $ {R}^2>0.9 $. Gradient boosted tree model was also used to identify key material properties influencing classification of $ {k}_L $, namely lattice energy per atom, atom density, band gap, mass density, and ratio of oxygen by transition metal atoms. Only fundamental materials properties describing the crystal symmetry, compound chemistry, and interatomic bonding were used in the classification process, which can be readily used in the initial phases of materials design. The proposed two-step process addresses the problem of small datasets and improves the predictive accuracy. The ML approach adopted in the present work is generic in nature and can be combined with high-throughput computing for the rapid discovery of new materials for specific applications.

With the development of affordable aberration correctors, analytical scanning transmission electron microscopy (STEM) studies of complex interfaces can now be conducted at high spatial resolution at laboratories worldwide. Energy-dispersive X-ray spectroscopy (EDS) in particular has grown in popularity, as it enables elemental mapping over a wide range of ionization energies. However, the interpretation of atomically resolved data is greatly complicated by beam–sample interactions that are often overlooked by novice users. Here we describe the practical factors—namely, sample thickness and the choice of ionization edge—that affect the quantification of a model perovskite oxide interface. Our measurements of the same sample, in regions of different thickness, indicate that interface profiles can vary by as much as 2–5 unit cells, depending on the spectral feature. This finding is supported by multislice simulations, which reveal that on-axis maps of even perfectly abrupt interfaces exhibit significant delocalization. Quantification of thicker samples is further complicated by channeling to heavier sites across the interface, as well as an increased signal background. We show that extreme care must be taken to prepare samples to minimize channeling effects and argue that it may not be possible to extract atomically resolved information from many chemical maps.

In a hot forming process, the study of the interface tool/product proves important. This study focuses on the influence of the third body in the case of pin-on-disc in an open contact. The objective of this work was to identify the third body-particle circulation mechanisms at high temperatures. The “wear and friction” tests were conducted with an open sliding contact on pairs of X40CrMoV5/Fe360B steels under a normal force of 70 N at 600 °C and with a speed of rotation of the disc of 50 rev/min. The pin material was X40CrMoV5 (AISI H13) steel and the disc material was Fe360B steel. Scanning electronic microscope, energy-dispersive spectroscopy (EDS), and X-ray diffractometer explored the development surface damage and oxides tribo-oxides. It was concluded that various types of the third body particles were present in the contact. The wear mechanism on the X40CrMoV5 pin in a high temperature contact is proposed.

A nanoscale and pure, olivine-structured LiFePO4 was synthesized at ∼300 °C using an organic–inorganic steric entrapment method. Normally, when calcined and crystallized in air, this method leads to the synthesis of compounds where the cations are in their highest oxidation state. However, in this study, we found a way to produce compounds having lower oxidation states (e.g., compounds containing Fe2+), which may have wider applications in the synthesis of other compounds with complex chemistry that have variable oxidation states and, therefore, potential applications in electronic ceramics. The resulting LiFePO4 or (Li2O·2FeO·P2O5) was characterized by thermogravimetric analysis/differential thermal analysis, x-ray diffractometry, scanning electron microscopy, transmission electron microscopy, inductively coupled plasma emission spectroscopy, specific surface area by Brunauer–Emmett–Teller nitrogen absorption, and particle size analysis.

Engineered nanomaterials (ENMs) strongly interact with biomolecules and cells due to their similar size scales. Consequently, ENMs are beginning to emerge as new medical diagnostic tools, probes in cell biology, and delivery vehicles, compelling us to understand the interactions at the nano-bio interface. Optical spectroscopic tools are excellent probes to characterize ENMs and investigate their interactions with complex biological systems, including biomolecules, cells, and even whole animals alike. Here, we discuss the role of many optical spectroscopic techniques such as fluorescence, Raman, surface plasmon, and infrared spectroscopy in elucidating nano-bio interactions. While these spectroscopic tools have the ability to provide valuable information on ENM distribution in biosystems, ENM interaction with proteins, and the mechanisms by which ENMs elicit an adverse physiological response, there are many challenges that remain to be addressed to improve their scope, resolution, and throughput.

The effects of stearic acid on the high-energy ball milling of tin powder have been investigated. The mean crystallite sizes, microstrain, and phase transformations were examined using different techniques like x-ray diffraction (XRD), Rietveld refinement method, and differential scanning calorimetry (DSC). After 28 h of milling, the Rietveld analysis showed the stabilization of Sn mean crystallite sizes at around 50 nm. Due to the presence of oxygen in stearic acid, the milling process gradually produced an amorphous Sn oxide phase. The DSC thermogram of the sample milled for 28 h showed two exothermic peaks separated by an endothermic peak. Based on the DSC measurements, two samples were annealed at 240 and 350 °C for 20 min. The annealing at 240 °C confirmed the presence of an amorphous phase which crystallized in nanostructured tetragonal SnO phase. The annealing at 350 °C revealed the nucleation of nanostructured tetragonal SnO2 phase.

Ca3Co4O9 and Ca2.8Bi0.2Co4O9 thin films were fabricated on LaAlO3 (LAO) substrate using pulsed laser deposition technique and were studied for their thermoelectric (TE) properties in Stranski–Krastanov mode for the first time. The thin films consisted of 3D clusters/islands on a ∼14-nm thick 2D layer with cluster density being higher for Ca2.8Bi0.2Co4O9 thin films. The clusters also represent areas of dislocation and therefore act as carrier scattering centers, which leads to a temperature-activated type conductivity. Seebeck coefficient as high as 136 and 163 μ V/K was measured for the Ca3Co4O9 and Ca2.8Bi0.2Co4O9 thin films, respectively, which is among the highest reported values for this system. The 3D island formation was also found to be useful in reducing the thermal conductivity of the thin film/substrate system by increased phonon scattering. This work shows that the island formation in thin films can be utilized as a means of enhancing TE properties of a thin film system, however, a detailed work including optimization of the film thickness and cluster/inland density is required.

A single layer of LaAlO3 with a nominal thickness of one unit cell, which is sandwiched between a SrTiO3 substrate and a SrTiO3 capping layer, is quantitatively investigated by high-resolution transmission electron microscopy. By the use of an aberration-corrected electron microscope and by employing sophisticated numerical image simulation procedures, significant progress is made in two aspects. First, the structural as well as the chemical features of the interface are determined simultaneously on an atomic scale from the same specimen area. Second, the evaluation of the structural and chemical data is carried out in a fully quantitative way on the basis of the absolute image contrast, which has not been achieved so far in materials science investigations using high-resolution electron microscopy. Considering the strong influence of even subtle structural details on the electronic properties of interfaces in oxide materials, a fully quantitative interface analysis, which makes positional data available with picometer precision together with the related chemical information, can contribute to a better understanding of the functionality of such interfaces.

The influence of a lack of sufficient electrical conductivity on the results of quantitative electron probe microanalysis has been investigated on a number of oxides. The effect of surface charging and the way it alters the emitted X-ray signals has been studied. It is shown that the presence of conducting coatings, such as carbon or copper, will affect the interelement X-ray intensity ratios, whatever the thickness of the coating may be. Although the effects for heavier elements may be acceptable, they cannot be ignored for a light element such as oxygen, where strong variations with coating thickness were observed. Quantitative analyses of oxygen, on uncoated well-conducting oxide specimens, using uncoated well-conducting hematite (Fe2O3) as a standard yielded excellent results in the range between 4 and 40 kV with the φ(ρz) software used. As soon as coated nonconducting specimens were examined, using the same hematite standard, coated under exactly the same conditions, widely scattering and noncoherent results were obtained. These discrepancies can only be attributed to a lack of conductivity.

High-throughput synthesis and characterization techniques have been effective in discovering new materials and performing rapid mapping of phase diagrams. The application of the combinatorial strategy to explore doped transition-metal oxides has led to the discovery of a transparent room-temperature ferromagnetic oxide in Co-doped anatase TiO2. The discovery has triggered a wave of studies into other metal oxide systems in pursuit of diluted magnetic semiconductors. In this article, we describe recent combinatorial studies of magnetic transition-metal oxides, germanium-based magnetic semiconductors, and Heusler alloys.

This introductory article provides the background for the September 2003 issue of MRS Bulletin on Ultrahigh-Temperature Materials for Jet Engines. It covers the need for these materials, the history of their development, and current challenges driving continued research and development. The individual articles that follow review achievements in four different material classes (three in situ composites—based on molybdenum silicide, niobium silicide, and silicon carbide, respectively—and high-melting-point platinum-group-metal alloys), as well as advances in coating systems developed both for oxidation protection and as thermal barriers. The articles serve as a benchmark to illustrate the progress made to date and the challenges ahead for ultrahigh-temperature jet-engine materials.

Elevated temperature scanning tunneling microscopy is used to study oxides that are room temperature insulators but become sufficiently electrically conducting at higher temperatures to allow imaging to be performed. Atomic resolution images of NiO, CoO, and UO2 have been obtained in this fashion which allow surface structure and defect determination. To complement the experiments, modeling of the electronic surface structure reveals which atomic sites give rise to the contrast observed in the images. Low voltage scanning electron microscopy is used to image small equilibrium pores in UO2 single crystals to evaluate the surface energy ratio of the (111) to (001) surfaces.