Interactions between trivalent rare earth oxides and mixed [Hbet][Tf2N]:H2O systems in the development of a one-step process for the separation of light from heavy rare earth elements

The factors, including ionic liquid:water ratios, temperature, solvent:solute contact times, and the effect of dissolved rare earth metal ions on the [Hbet][Tf2N]:H2O thermometric phase change are determined to develop a process for separating the light from the heavy rare earth metal oxides in [Hbet][Tf2N]:H2O mixtures. The relative solubility data for three light (La2O3, Nd2O3, and Eu2O3), two heavy (Y2O3 and Yb2O3) rare earth metal oxides (REOs), and Gd2O3 at different temperatures and different solute:solvent contact times are reported for 1:1 [Hbet][Tf2N]:H2O. The light REOs dissolve easily at 57 °C with the La and Eu reaching maximum solubility within minutes while the heavy REOs have very low solubilities at this temperature with negligible amounts being dissolved for contact times less than 80 min. Gd2O3 dissolves more slowly than the La, Eu, and Nd oxides at 57 °C reaching maximum solubility only after 160 min. Changing the [Hbet][Tf2N]:H2O ratio from 1:1 to 16:1 increases the time required to dissolve the REOs. The times taken to reach maximum solubility decrease for all of the REOs up to 95 °C, resulting in the separations between the light and heavy rare earth elements, and Gd becoming less distinct. The presence of rare earth metal ions in [Hbet][Tf2N]:H2O results in a reduction in the upper critical solution temperature (UCST) of the solvent from 55.6 °C to as low as 31.8 °C with Gd3+. The best separation of light from heavy REOs is achieved at 57 °C but better separation of Gd from the light REOs is achieved at 40 °C, below the solvent UCST. The best conditions for a one-step separation of light from heavy REOs in [Hbet][Tf2N]:H2O mixtures is achieved with 1:1 [Hbet][Tf2N]:H2O at 57 °C using short contact oxide:solvent times (maximum 5 min). Separations of light from heavy REOs, in waste phosphor samples, containing La2O3, CeO2, Eu2O3, Gd2O3, Tb3O4 and Y2O3, are also achieved even in the presence of high concentrations of heavy REOs using short contact times. The use of [Hbet][Tf2N]:H2O as a means of separating light and heavy REOs is aided by the ease of recycling the solvent which can be recycled and reused at least five times with little loss of solvent quality or efficiency

Investigation of the fluid behavior of asphaltenes and toluene insolubles by high-temperature proton nuclear magnetic resonance and rheometry and their application to visbreaking

The fluid behavior of asphaltenes at elevated temperatures impacts coke formation in a number of hydrocarbon conversion processes, including visbreaking and delayed coking. In this study, the asphaltenes from a number of sources, namely, a vacuum residue, a petroleum source rock (Kimmeridge clay) bitumen obtained by hydrous pyrolysis, and bitumen products from a sub-bituminous coal and pine wood obtained by thermolytic solvent extraction using tetralin, have been characterized using high-temperature proton nuclear magnetic resonance (1H NMR), and the results correlated with those from small-amplitude oscillatory shear rheometry. Further for comparison, the coke (toluene insolubles) obtained from visbreaking the vacuum residue was also characterized. All of the asphaltenes became completely fluid by 300 °C, with hydrogen being completely mobile with coke formation, identified as a solid phase, not occurring to a significant extent until 450 °C. Extremely good agreement was obtained between high-temperature 1H NMR and rheometry results, which confirmed that the asphaltenes were highly fluid from 300 °C, with initial signs of resolidification being observed at temperatures of around 450 °C. During softening, extremely good correlations between fluid hydrogen and phase angle were obtained as the asphaltenes softened. The toluene insolubles however did contain some fluid material; thus, it cannot be regarded as strictly solid coke, but clearly, with increasing temperature, the fluid material did convert to coke. Under actual process conditions, this fluid material could be responsible for coke adhering to reactor surfaces

Phase Transition in the Number Partitioning Problem

Number partitioning is an NP-complete problem of combinatorial optimization. A statistical mechanics analysis reveals the existence of a phase transition that separates the easy from the hard to solve instances and that reflects the pseudo-polynomiality of number partitioning. The phase diagram and the value of the typical ground state energy are calculated.Comment: minor changes (references, typos and discussion of results

NASA space station automation: AI-based technology review. Executive summary

Research and Development projects in automation technology for the Space Station are described. Artificial Intelligence (AI) based technologies are planned to enhance crew safety through reduced need for EVA, increase crew productivity through the reduction of routine operations, increase space station autonomy, and augment space station capability through the use of teleoperation and robotics

Analysis of breeding and pathology helps refine management practices of a large-scale N '-ethyl-N '-nitrosourea mouse mutagenesis programme

N'-ethyl-N'-nitrosourea (ENU) is a powerful germline mutagen used in conjunction with phenotype-driven screens to generate novel mouse mutants. ENU also induces genetic lesions in somatic cells and dosage requires optimization between maximum germline mutation rate versus induced sterility and tumourigenesis that compromise the welfare and fecundity of the ENU-treated males. Here, we present our experience with BALB/cAnNCr1 and C57BL/6J mice in terms of the pathology induced by ENU and its impact on breeding. In both mouse strains, morbidity and mortality rises with ENU dose. In more than 75% of C571BL/6J males, morbidity and mortality were attributable to the development of malignant T-lymphoblastic lymphoma. Approximately 50% of ENIJI-treated BALB/cAnNCr1 males develop early malignant T-lymphoblastic lymphoma, but the cohort that survives develops late-onset lung carcinoma. Within strains, the latency of these clinically important tumour(s) was not dosage-dependent, but the proportion of mice developing tumours and consequently removed from the breeding programme increased with ENU dosage. The median number of offspring per ENU-treated C57BL/6J male in standard matings with C3H/HeH females decreased with increasing dosage. The two most important underlying causes for lower male fecundity were increased infertility in the highest dosage group and reduced numbers of litters born to the remaining fertile C57BL/6J males due to a higher incidence of morbidity. These findings have allowed us to refine breeding strategy. To maximize the number of offspring from each ENU-treated male, we now rotate productive males between two cages to expose them to more females. This optimizes the number of mutation carrying offspring while reducing the number of ENU-treated males that must be generated.</p

All-electron magnetic response with pseudopotentials: NMR chemical shifts

A theory for the ab initio calculation of all-electron NMR chemical shifts in insulators using pseudopotentials is presented. It is formulated for both finite and infinitely periodic systems and is based on an extension to the Projector Augmented Wave approach of Bloechl [P. E. Bloechl, Phys. Rev. B 50, 17953 (1994)] and the method of Mauri et al [F. Mauri, B.G. Pfrommer, and S.G. Louie, Phys. Rev. Lett. 77, 5300 (1996)]. The theory is successfully validated for molecules by comparison with a selection of quantum chemical results, and in periodic systems by comparison with plane-wave all-electron results for diamond.Comment: 25 pages, 4 tables, submitted to Physical Review

The dynamics of proving uncolourability of large random graphs I. Symmetric Colouring Heuristic

We study the dynamics of a backtracking procedure capable of proving uncolourability of graphs, and calculate its average running time T for sparse random graphs, as a function of the average degree c and the number of vertices N. The analysis is carried out by mapping the history of the search process onto an out-of-equilibrium (multi-dimensional) surface growth problem. The growth exponent of the average running time is quantitatively predicted, in agreement with simulations.Comment: 5 figure

Mutation at the Evi1 locus in Junbo mice causes susceptibility to otitis media

Otitis media ( OM), inflammation of the middle ear, remains the most common cause of hearing impairment in children. It is also the most common cause of surgery in children in the developed world. There is evidence from studies of the human population and mouse models that there is a significant genetic component predisposing to OM, yet nothing is known about the underlying genetic pathways involved in humans. We identified an N-ethyl-N-nitrosourea-induced dominant mouse mutant Junbo with hearing loss due to chronic suppurative OM and otorrhea. This develops from acute OM that arises spontaneously in the postnatal period, with the age of onset and early severity dependent on the microbiological status of the mice and their air quality. We have identified the causal mutation, a missense change in the C-terminal zinc finger region of the transcription factor Evi1. This protein is expressed in middle ear basal epithelial cells, fibroblasts, and neutrophil leukocytes at postnatal day 13 and 21 when inflammatory changes are underway. The identification and characterization of the Junbo mutant elaborates a novel role for Evi1 in mammalian disease and implicates a new pathway in genetic predisposition to OM