Abstract: Controlled in-plane rotation of the magnetic easy axis in manganite heterostructures by tailoring the interface oxygen network could allow the development of correlated oxide-based magnetic tunnelling junctions with non-collinear magnetization, with possible practical applications as miniaturized high-switching-speed magnetic random access memory (MRAM) devices. Here, we demonstrate how to manipulate magnetic and electronic anisotropic properties in manganite heterostructures by engineering the oxygen network on the unit-cell level. The strong oxygen octahedral coupling is found to transfer the octahedral rotation, present in the NdGaO3 (NGO) substrate, to the La2/3Sr1/3MnO3 (LSMO) film in the interface region. This causes an unexpected realignment of the magnetic easy axis along the short axis of the LSMO unit cell as well as the presence of a giant anisotropic transport in these ultrathin LSMO films. As a result we possess control of the lateral magnetic and electronic anisotropies by atomic-scale design of the oxygen octahedral rotation.

Abstract: Lithium-ion battery cathode materials have relied on cationic redox reactions until the recent discovery of anionic redox activity in Li-rich layered compounds which enables capacities as high as 300 mAh g(-1). In the quest for new high-capacity electrodes with anionic redox, a still unanswered question was remaining regarding the importance of the structural dimensionality. The present manuscript provides an answer. We herein report on a beta-Li2IrO3 phase which, in spite of having the Ir arranged in a tridimensional (3D) framework instead of the typical two-dimensional (2D) layers seen in other Li-rich oxides, can reversibly exchange 2.5 e(-) per Ir, the highest value ever reported for any insertion reaction involving d-metals. We show that such a large activity results from joint reversible cationic (Mn+) and anionic (O-2)(n-) redox processes, the latter being visualized via complementary transmission electron microscopy and neutron diffraction experiments, and confirmed by density functional theory calculations. Moreover, beta-Li2IrO3 presents a good cycling behaviour while showing neither cationic migration nor shearing of atomic layers as seen in 2D-layered Li-rich materials. Remarkably, the anionic redox process occurs jointly with the oxidation of Ir4+ at potentials as low as 3.4 V versus Li+/Li-0, as equivalently observed in the layered alpha-Li2IrO3 polymorph. Theoretical calculations elucidate the electrochemical similarities and differences of the 3D versus 2D polymorphs in terms of structural, electronic and mechanical descriptors. Our findings free the structural dimensionality constraint and broaden the possibilities in designing high-energy-density electrodes for the next generation of Li-ion batteries.

Abstract: 'Colossal magnetoresistance' in perovskite manganites such as La0.7Ca0.3MnO3 (LCMO), is caused by the interplay of ferro-paramagnetic, metal-insulator and structural phase transitions. Moreover, different electronic phases can coexist on a very fine scale resulting in percolative electron transport. Here we report on (LCMO)(1-x):(MgO)(x) (0 < x less than or equal to 0.8) epitaxial nano-composite films in which the structure and magnetotransport properties of the manganite nanoclusters can be tuned by the tensile stress originating from the MgO second phase. With increasing x, the lattice of LCMO was found to expand, yielding a bulk tensile strain. The largest colossal magnetoresistance of 10(5)% was observed at the percolation threshold in the conductivity at x(c) approximate to 0.3, which is coupled to a structural phase transition from orthorhombic (0 < x less than or equal to 0.1) to rhombohedral R (3) over barc structure (0.33 less than or equal to x less than or equal to 0.8). An increase of the Curie temperature for the R (3) over barc phase was observed. These results may provide a general method for controlling the magnetotransport properties of manganite-based composite films by appropriate choice of the second phase.

Abstract: It is widely accepted that the physical properties of nanostructures depend on the type of surface facets1, 2. For Au nanorods, the surface facets have a major influence on crucial effects such as reactivity and ligand adsorption and there has been controversy regarding facet indexing3, 4. Aberration-corrected electron microscopy is the ideal technique to study the atomic structure of nanomaterials5, 6. However, these images correspond to two-dimensional (2D) projections of 3D nano-objects, leading to an incomplete characterization. Recently, much progress was achieved in the field of atomic-resolution electron tomography, but it is still far from being a routinely used technique. Here we propose a methodology to measure the 3D atomic structure of free-standing nanoparticles, which we apply to characterize the surface facets of Au nanorods. This methodology is applicable to a broad range of nanocrystals, leading to unique insights concerning the connection between the structure and properties of nanostructures.

Abstract: Although Li-rich layered oxides (Li1+xNiyCozMn1−x−y−zO2 > 250 mAh g−1) are attractive electrode materials providing energy densities more than 15% higher than todays commercial Li-ion cells, they suffer from voltage decay on cycling. To elucidate the origin of this phenomenon, we employ chemical substitution in structurally related Li2RuO3 compounds. Li-rich layered Li2Ru1−yTiyO3 phases with capacities of ~240 mAh g−1 exhibit the characteristic voltage decay on cycling. A combination of transmission electron microscopy and X-ray photoelectron spectroscopy studies reveals that the migration of cations between metal layers and Li layers is an intrinsic feature of the chargedischarge process that increases the trapping of metal ions in interstitial tetrahedral sites. A correlation between these trapped ions and the voltage decay is established by expanding the study to both Li2Ru1−ySnyO3 and Li2RuO3; the slowest decay occurs for the cations with the largest ionic radii. This effect is robust, and the finding provides insights into new chemistry to be explored for developing high-capacity layered electrodes that evade voltage decay.

Abstract: In this work, the effect of geometry and orientation of food cans on the heating characteristics of processed liquid foods and the resulting lethality target values as a function of the processing times have been investigated. For this purpose, the governing differential equations have been solved numerically for elliptical and cylindrical cans of varying aspect ratios in different orientations in order to delineate their effect on the heating rate (especially of the slowest heating zone [SHZ]) and lethality values over wide ranges of rheological features including shear thinning (n < 1), Newtonian (n = 1), and shear thickening (n > 1) behaviors. The flow and heat transfer characteristics were analyzed with the help of velocity vectors, isotherm contours, average Nusselt number, SHZ temperature and heat penetration parameters, and lethality target values. Also, comparisons were made in terms of the sterilization time and heat penetration parameters to identify the preferable geometries and orientations of food cans for effective heating of non-Newtonian foodstuffs. Finally, favorable conditions in terms of the shape and orientation of the can and the rheological properties have been delineated which lead to superior heating characteristics. Practical Applications Processed foodstuffs are produced in various forms ranging from that in solid, liquid, or as heterogeneous mixtures. Often such liquid and heterogeneous suspensions products are viscous non-Newtonian in character and their thermal processing (including pasteurization, sterilization, etc.) tends to be much more challenging than that of their Newtonian counterparts like air and water. This work explores heating of non-Newtonian liquid foodstuffs in cans of various shapes, geometries and in different orientations in the free convection regime. The results show that depending upon the rheological properties of the products, some orientations and/or geometries offer potential advantages in terms of shorter processing times and lethality values. This information can be of great potential in customizing the design of containers for different food products as well as of different rheological properties.

Abstract: The reactivity of platinized ultramicroelectrodes (Pt-black UMEs) towards superoxide anion O-2(.-), an unstable Reactive Oxygen Species (ROS), and its relatives, H2O2 and O-2, was studied. Voltammetric studies in PBS demonstrate that Pt-black UMEs provide: i) a well-resolved reversible redox signature for O-2(.-) detected in both alkaline and physiological buffers (pH 12 and 7.4); ii) irreversible oxidation and reduction waves for H2O2 at pH 7.4. The oxygen reduction reaction (ORR) at Pt-black surfaces solely yields H2O2 (2 electrons/2 H+) at physiological pH. Consequently, Pt-black UMEs allow to sense different ROS including superoxide anion for future biomedical or physico-chemical investigations.

Abstract: The number and composition of species in a community can be quantified with alpha-diversity indices, including species richness (R), Simpson's index (D), and the Shannon-Wiener index (HGREEK TONOS). In forest communities, there are large variations in tree size among species and individuals of the same species, which result in differences in ecological processes and ecosystem functions. However, tree size inequality (TSI) has been largely neglected in studies using the available diversity indices. The TSI in the diameter at breast height (DBH) data for each of 999 20 m x 20 m forest census quadrats was quantified using the Gini index (GI), a measure of the inequality of size distribution. The generalized performance equation was used to describe the rotated and right-shifted Lorenz curve of the cumulative proportion of DBH and the cumulative proportion of number of trees per quadrat. We also examined the relationships of alpha-diversity indices with the GI using correlation tests. The generalized performance equation effectively described the rotated and right-shifted Lorenz curve of DBH distributions, with most root-mean-square errors (990 out of 999 quadrats) being < 0.0030. There were significant positive correlations between each of three alpha-diversity indices (i.e., R, D, and H') and the GI. Nevertheless, the total abundance of trees in each quadrat did not significantly influence the GI. This means that the TSI increased with increasing species diversity. Thus, two new indices are proposed that can balance alpha-diversity against the extent of TSI in the community: (1 – GI) x D, and (1 – GI) x H'. These new indices were significantly correlated with the original D and HGREEK TONOS, and did not increase the extent of variation within each group of indices. This study presents a useful tool for quantifying both species diversity and the variation in tree sizes in forest communities, especially in the face of cumulative species loss under global climate change.

Abstract: Ptychography provides highly efficient imaging in scanning transmission electron microscopy (STEM), but questions have remained over its applicability to strongly scattering samples such as those most commonly seen in materials science. Although contrast reversals can appear in ptychographic phase images as the projected potentials of the sample increase, we show here how these can be easily overcome by a small amount of defocus. The amount of defocus is small enough that it not only can exist naturally when focusing using the annular dark field (ADF) signal but can also be adjusted post acquisition. The ptychographic images of strongly scattering materials are clearer at finite doses than other STEM techniques and can better reveal light atomic columns within heavy lattices. In addition, data for ptychography can now be collected simultaneously with the fastest of ADF scans. This combination of sensitivity and interpretability presents an ideal workflow for materials science.

Abstract: As of 2017, the sale and use of the refrigerants most commonly used in automotive cooling systems – hydrofluorocarbons – are entirely banned in all new vehicles placed on the market in the European Union. These refrigerants have been recognised as potent greenhouse gases and, therefore, direct contributors to climate change. It is within this regulation-driven market that the technologies for a sustainable solution have been developed. However, this paper argues that the market for automotive cooling systems has been 'locked-in', which means that competing technologies, operating under dynamic increasing returns, will allow for one – potentially inferior technology – to dominate the market. Whilst such a situation is not uncommon, this paper discusses the way that regulation has reinforced a patented monopoly in 'picking winners': to the advantage of a synthetic chemical, R-1234yf, as opposed to the natural solution, which is CO2. By developing a generic conceptual framework of path dependence and lock-in, the presented evidence seeks to show how a snowballing effect has led to the intensification of differences in market share. We also argue that the automotive industry is potentially promoting short-term fixes, rather than long-term, sustainable and economically viable solutions. (C) 2017 Elsevier Ltd. All rights reserved.

Abstract: Resource recovery and reuse from domestic wastewater has become an important subject for the current development of sanitation technologies and infrastructures. Different technologies are available and combined into sanitation concepts, with different performances. This study provides a methodological approach to evaluate the sustainability of these sanitation concepts with focus on resource recovery and reuse. St. Eustatius, a small tropical island in the Caribbean, was used as a case study for the evaluation. Three source separation-communityon-site and two combined sewerage island-scale concepts were selected and compared in terms of environmental (net energy use, nutrient recovery/reuse, BOD/COD, pathogens, and GHG emission, land use), economic (CAPEX and OPEX), social cultural (acceptance, required competences and education), and technological (flexibility/ adaptability, reliability/continuity of service) indicators. The best performing concept, is the application of Upflow Anaerobic Sludge Bed (UASB) and Trickling Filter (TF) at island level for combined domestic wastewater treatment with subsequent reuse in agriculture. Its overall average normalised score across the four categories (i. e., average of average per category) is about 15% (0.85) higher than the values of the remaining systems and with a score of 0.73 (conventional activated sludge – centralised level), 0.77 (UASB-septic tank (ST)), 0.76 (UASB-TF – community level), and 0.75 (ST – household level). The higher score of the UASB-TF at community level is mainly due to much better performance in the environmental and economic categories. In conclusion, the case study provides a methodological approach that can support urban planning and decision-making in selecting more sustainable sanitation concepts, allowing resource recovery and reuse in small island context or in other contexts.

Abstract: Appropriate assessment of firm sustainability facilitates actor-driven processes towards sustainable development. The methodology in this paper builds further on two proven methodologies for the assessment of sustainability performance: it combines the sustainable value approach with frontier efficiency benchmarks. The sustainable value methodology tries to relate firm performance to the use of different resources. This approach assesses contributions to corporate sustainability by comparing firm resource productivity with the resource productivity of a benchmark, and this for all resources considered. The efficiency is calculated by estimating the production frontier indicating the maximum feasible production possibilities. In this research, the sustainable value approach is combined with efficiency analysis methods to benchmark sustainability assessment. In this way, the production theoretical underpinnings of efficiency analysis enrich the sustainable value approach. The methodology is presented using two different functional forms: the CobbDouglas and the translog functional forms. The simplicity of the CobbDouglas functional form as benchmark is very attractive but it lacks flexibility. The translog functional form is more flexible but has the disadvantage that it requires a lot of data to avoid estimation problems. Using frontier methods for deriving firm specific benchmarks has the advantage that the particular situation of each company is taken into account when assessing sustainability. Finally, we showed that the methodology can be used as an integrative sustainability assessment tool for policy measures.

Abstract: The crystal structure of the K6.4Nb28.2Ta8.1O94 pseudo-tetragonal tungsten bronze-type oxide was determined using a combination of X-ray powder diffraction, neutron diffraction and transmission electron microscopy techniques, including electron diffraction, high angle annular dark field scanning transmission electron microscopy (HAADF-STEM), annular bright field STEM (ABF-STEM) and energy-dispersive X-ray compositional mapping (STEM-EDX). The compound crystallizes in the space group Pbam with unit cell parameters a = 37.468(9) A, b = 12.493(3) A, c = 3.95333(15) A. The structure consists of corner sharing (Nb,Ta)O6 octahedra forming trigonal, tetragonal and pentagonal tunnels. All tetragonal tunnels are occupied by K(+) ions, while 1/3 of the pentagonal tunnels are preferentially occupied by Nb(5+)/Ta(5+) and 2/3 are occupied by K(+) in a regular pattern. A fractional substitution of K(+) in the pentagonal tunnels by Nb(5+)/Ta(5+) is suggested by the analysis of the HAADF-STEM images. In contrast to similar structures, such as K2Nb8O21, also parts of the trigonal tunnels are fractionally occupied by K(+) cations.