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1.
Lithium Insertion Mechanism in Iron-Based Oxyfluorides with Anionic Vacancies Probed by PDF Analysis
Dr. Damien Dambournet Dr. Karena W Chapman Dr. Mathieu Duttine Dr. Olaf Borkiewicz Dr. Peter J Chupas Dr. Henri Groult 《ChemistryOpen》2015,4(4):443-447
The mechanism of lithium insertion that occurs in an iron oxyfluoride sample with a hexagonal–tungsten–bronze (HTB)-type structure was investigated by the pair distribution function. This study reveals that upon lithiation, the HTB framework collapses to yield disordered rutile and rock salt phases followed by a conversion reaction of the fluoride phase toward lithium fluoride and nanometer-sized metallic iron. The occurrence of anionic vacancies in the pristine framework was shown to strongly impact the electrochemical activity, that is, the reversible capacity scales with the content of anionic vacancies. Similar to FeOF-type electrodes, upon de-lithiation, a disordered rutile phase forms, showing that the anionic chemistry dictates the atomic arrangement of the re-oxidized phase. Finally, it was shown that the nanoscaling and structural rearrangement induced by the conversion reaction allow the in situ formation of new electrode materials with enhanced electrochemical properties. 相似文献
2.
Jigneshkumar P. Patel Zou Guo Xiang Shaw Ling Hsu Andrew B. Schoch Sena Ada Carleen Dean Matsumoto 《Journal of Polymer Science.Polymer Physics》2015,53(21):1519-1526
A uniform dispersion of reactants is necessary to achieve a complete reaction involving multicomponents. In this study, we have examined the role of plasticizer in the reaction of two seemingly unlikely reactants: a highly crystalline hexamethylenetetramine (HMTA) and a strongly hydrogen bonded phenol formaldehyde resin. By combining information from NMR, infrared spectroscopy and differential scanning calorimetry, we were able to determine the role of specific intermolecular interactions necessary for the plasticizer to dissolve the highly crystalline HMTA and to plasticize the phenol formaldehyde resin in this crosslinking reaction. The presence of the plasticizer increased the segmental mobility, disrupted the hydrogen bonded matrix, and freed the hydroxyl units, which further increased the solubility of the HMTA. Both the endothermic and exothermic transitions are accounted for in the calorimetric data obtained. For the first time, it is possible to obtain the effective molar ratio of each component needed to complete the crosslinking reaction efficiently. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1519–1526 相似文献
3.
A rectilinear drawing of a graph is one where each edge is drawn as a straight-line segment, and the rectilinear crossing number of a graph is the minimum number of crossings over all rectilinear drawings. We describe, for every integer k ≥ 4, a class of graphs of crossing number k, but unbounded rectilinear crossing number. This is best possible since the rectilinear crossing number is equal to the crossing number whenever the latter is at most 3. Further, if we consider drawings where each edge is drawn as a polygonal line segment with at most one break point, then the resulting crossing number is at most quadratic in the regular crossing number. © 1993 John Wiley & Sons, Inc. 相似文献
4.
Dean A. Carlson 《Journal of Mathematical Analysis and Applications》2002,276(2):561-588
The method of equivalent variational methods, originally due to Carathéodory for free problems in the calculus of variations is extended to investigate feedback Nash equilibria for a class of n-person differential games. Both the finite-horizon and infinite-horizon cases are considered. Examples are given to illustrate the presented results. 相似文献
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The bias dependent interface charge is considered as the origin of the observed non-ideality in current–voltage and capacitance–voltage characteristics. Using the simplified model for the interface electronic structure based on defects interacting with the continuum of interface states, the microscopic origin of empirical parameters describing the bias dependent interface charge function is investigated. The results show that in non-ideal metal–semiconductor contacts the interface charge function depends on the interface disorder parameter, density of defects, barrier pinning parameter and the effective gap center. The theoretical predictions are tested against several sets of published experimental data on bias dependent ideality factor and excess capacitance in various metal–semicoductor systems. 相似文献
7.
Shigenori Okada Shigemitsu Yoshida Shahid H Ashrafi Dean E Schraufnagel 《Microscopy and microanalysis》2002,8(2):104-115
Osteocytes communicate through a canalicular system that maintains the vitality and mineral metabolism of bone. Casting the vascular canals and canaliculi of compact bone with methacrylate and viewing them with scanning electron microscopy shows their extent and relationships. Confocal laser scanning microscopy of the same specimen before corrosion establishes the degree of calcification of the different tissue components. These methods were used to compare basal with alveolar compact bone in the rat mandible at different ages. Sections of the mandibular molar region were placed in a methacrylate resin. After polymerization and study with confocal microscopy, the organic matrix was removed. Juvenile rats had large irregular central vascular canals and lacunae that were more concentric in the basal than the alveolar bone. Cast lacunae were round, and the canaliculi from these lacunae were short and thick in both bones. Adult rats had regular concentrically arranged lacunae in the basal bone. Cast lacunae were ellipsoid and flatter in the basal bone than in the alveolar bone. The intercommunicating canaliculi were increased and canaliculi had more branching than the juvenile rats. The aged rats had fewer vascular canals, lacunae, and canaliculi and had osteoporotic changes. The cast lacunae were slender and flat especially in the basal bone. The porosity of the mandible became more pronounced in the alveolar than in the basal bone with aging. The canaliculi of mandibular compact bone thinned and developed extensive branching with adulthood but decreased in size and number with advanced age. Lacunae proceed from the large circular structures of youth to the flat forms of the aged. These studies show that the internal structure of compact bone changes with age and mirrors its functional state. 相似文献
8.
9.
The Born scattering approximation has been widely used in seismology to study scattered waves, and to linearize the propagation problem for inversion. The standard Born theory requires the model be separated into a smooth, reference model and a perturbation. Scattering occurs from the pertubation. In the distorted Born approximation, when the reference model is inhomogeneous, the reference Green's functions are normally not known exactly, but the error in these Green's functions is rarely quantified. In this paper, we generalize Born scattering theory to include the errors in the Green's functions explicitly, and obtain scattering integrals from these errors. For forward modelling, there is no need to separate the model into a reference and perturbation part - approximate Green's functions in the true model can be used to calculate the scattered signals.
The theory is developed for inhomogeneous, anisotropic media. Asymptotic ray theory results are suitable approximate Green's functions for the generalized Born scattering theory. The error terms are simple, easily calculated and included in the scattering integrals. Various applications of generalized Born scattering theory have already appeared in the literature, e.g. quasi-shear ray coupling, and this paper is restricted to an improved and more complete theoretical development. Further applications will appear elsewhere. 相似文献