Evolution of Local Structural Ordering and Chemical Distribution upon Delithiation of a Rock Salt–Structured Li1.3Ta0.3Mn0.4O2 Cathode

Lithium‐rich disordered rock‐salt oxides have attracted great interest owing to their promising performance as Li‐ion battery cathodes. While experimental and theoretical efforts are critical in advancing this class of materials, a fundamental understanding of key property changes upon Li extraction is largely missing. In the present study, single‐crystal synthesis of a new disordered rock‐salt cathode material, Li_1.3Ta_0.3Mn_0.4O₂ (LTMO), and its use as a model compound to investigate Li concentration–driven evolution of local cationic ordering, charge compensation, and chemical distribution are reported. Through the combined use of 2D and 3D X‐ray nanotomography, it is shown that Li removal accompanied by oxygen oxidation is correlated with the development of morphological defects such as particle cracking. Chemical heterogeneity, quantified by subparticle level distribution of Mn valence state, is minimal during Mn redox, which drastically increases upon the formation of cracks during oxygen redox. Density functional theory and bond valence sum mismatch calculations reveal the presence of local short‐range ordering in the pristine oxide, which gradually disappears along with the extraction of Li. The study suggests that with cycling the transformation into true cation–disordered state can be expected, which likely impacts the voltage profile and obtainable energy density of the oxide cathodes.     

Capture of Organic Vapors Using Adsorption and Electrothermal Regeneration

Activated-carbon-fiber cloth (ACFC) is an alternative adsorbent to granular activated carbon (GAC) for removing and recovering organic vapors from gas streams. Electrothermal desorption (ED) of ACFC provides rapid regeneration while requiring less energy compared to traditional regeneration techniques used with GAC. This paper provides proof-of-concept results from a bench-scale ACFC adsorption system. The automated system captured 1,000 ppmv of hazardous air pollutants/volatile organic compounds (HAPs/VOCs) from air streams and demonstrated the use of ED, using ac voltage, to recover the HAP/VOC as a pure liquid. The desorbed HAP/VOC condensed onto the inner walls of the adsorber and was collected at the bottom of the vessel, without the use of ancillary cooling. Seventy percent of the HAP/VOC was collected per cycle as condensate, with the balance being retained in the regenerated adsorber or recycled to the second adsorber. ED with in-vessel condensation results in minimal N2 consumption and short regeneration cycle times allowing the process to be cost competitive with conventional GAC-based adsorption processes. This technology extends the application of carbon adsorption systems to situations that were previously economically and physically impractical.     

EXPLORING FOR FAN AND DELTA SANDSTONES IN THE OFFSHORE FALKLANDS BASINS

Four basins surround the Falkland Islands, but only the North Falkland Basin has been drilled; six wells were drilled there in 1998. Although all six wells encountered good quality sandstones, none of them targeted the basin margins, on what are now thought to be the optimum migration pathways associated with the basin's thick lacustrine source rocks. Subsequently, a 3D seismic survey acquired in 2004 was designed to identify potential basin-margin -derived sandstones entering the basin along transfer zones. From this survey, a number of basin-margin -attached fans have been identified; these prograded into lacustrine waters of varying depths. These Early Cretaceous alluvial/fan delta/deep-lacustrine fan systems are interpreted to provide excellent potential reservoir facies as they are intimately associated with thick, mature source rocks. They will provide the focus for the next planned phase of exploration in the North Falkland Basin.
A phase of drilling is also planned for the basins to the south of the Islands, where large deltaic and fan systems, slightly younger than those imaged in the North Falkland Basin, are seen on seismic to prograde from the same Palaeozoic hinterland that produced the older, North Falkland Basin fans.
This paper attempts to show how sedimentary models derived from targeted seismic programmes following initial exploration can be utilised to plan and improve new drilling campaigns in a frontier basin. It presents an analysis of sediment dispersal patterns in basins of marine and lacustrine origin linked to a single hinterland area, and highlights the nature of the relationship between relay ramp/transfer zone development and sediment dispersal patterns in the subsurface.     

Autoimmunity caused by disruption of central T cell tolerance. A murine model of drug-induced lupus

A side effect of therapy with procainamide and numerous other medications is a lupus-like syndrome characterized by autoantibodies directed against denatured DNA and the (H2A-H2B)-DNA subunit of chromatin. We tested the possibility that an effect of lupus-inducing drugs on central T cell tolerance underlies these phenomena. Two intrathymic injections of procainamide-hydroxylamine (PAHA), a reactive metabolite of procainamide, resulted in prompt production of IgM antidenatured DNA antibodies in C57BL/6xDBA/2 F1 mice. Subsequently, IgG antichromatin antibodies began to appear in the serum 3 wk after the second injection and were sustained for several months. Specificity, inhibition and blocking studies demonstrated that the PAHA-induced antibodies showed remarkable specificity to the (H2A-H2B)-DNA complex. No evidence for polyclonal B cell activation could be detected based on enumeration of Ig-secreting B cells and serum Ig levels, suggesting that a clonally restricted autoimmune response was induced by intrathymic PAHA. The IgG isotype of the antichromatin antibodies indicated involvement of T cell help, and proliferative responses of splenocytes to oligonucleosomes increased up to 100-fold. As little as 5 microM PAHA led to a 10-fold T cell proliferative response to chromatin in short term organ culture of neonatal thymi. We suggest that PAHA interferes with self-tolerance mechanisms accompanying T cell maturation in the thymus, resulting in the emergence of chromatin-reactive T cells followed by humoral autoimmunity.     

Subreflector shaping to improve multiple-beam performance of a Cassegrain antenna

A method of designing multiple-beam antennas based on shaping the subreflector of an offset Cassegrain antenna is described. It is applied to a compact system having a diameter of 300? that is required to produce beams up to 4-6°either side of boresight. The performance is shown to be only slightly less than that obtainable by also shaping the main reflector, indicating that efficient multiple-satellite-access antennas can be designed without specially shaped main reflectors.     

Methodologies for the optimal design of parallel manipulators

In this paper the problem of determining a manipulator design so that its workspace corresponds to a prescribed workspace is considered. Two different strategies, resulting in two different types of optimization problem are considered. The first strategy attempts to obtain a good overall approximation to the prescribed workspace and results in an unconstrained optimization problem. The second strategy entails designing a manipulator so that its workspace fully encloses the prescribed workspace and results in a constrained optimization problem. Two specific formulations of the constrained problem are proposed. The first constrained problem simply aims to fit the manipulator workspace as exactly as possible to the prescribed workspace, while still ensuring that the prescribed workspace is fully enclosed. The second constrained optimization formulation is used to design a manipulator, the workspace of which fully encloses the prescribed workspace, but which is also well‐conditioned throughout the workspace with respect to some performance measure. The particular manipulator used to illustrate and evaluate these formulations is a simple 2‐dof planar parallel manipulator, and the final formulation is also applied to a 3‐dof planar parallel manipulator. Although the manipulators studied here are simple, the objective of this study is to obtain a robust numerical methodology which can be extended to more practical and complex manipulators. Copyright © 2003 John Wiley & Sons, Ltd.