X-ray structure analysis of poly[di-(3,4-dimethylphenoxy)phosphazene]

The crystal structure of oriented poly[di-(3,4-dimethylphenoxy) phosphazene] (PDMP) was determined by x-ray diffraction. Unit-cell parameters were found to be a = 15.85, b = 19.43, and c = 9.85 Å. The unit cell is metrically orthorhombic with monoclinic space group P2₁. There were 48 refinable diffraction spots in the observed reciprocal lattice region, of which 28 were observed and 20 were unobserved. A refined model yielded the following residuals: R^(obs) = 0.162 and 0.138. It was shown that a two-chain unit cell with a [T₃C]₂ (trans, trans, trans, cis, trans, trans, trans, cis) backbone conformation was the correct structure. The dimethylphenoxy side groups were arranged in nearly parallel planes, slightly off-normal to the fiber c axis. The polymer chains are extremely tightly packed and contain close but reasonable steric contacts.     

Measurement of static strain at 2,000° F

This paper describes the work being done at Hughes Aircraft Company using capacitance strain gages to measure static strains at temperatures up to and including 2,000° F. A new configuration of the capacitance gage is described with a gage length of 0.50 in. Methods of attaching the gage have been developed for welding, bonding and flame-spray installations. Instrumentation procedures and methods are defined. Statistical accuracy and test results are discussed on the results obtained from a lot of 60 gages. Results discussed were obtained on Rene 41, titanium and L605 stainless steel. Data analysis on the gage includes gage factor, gage factor vs. temperature, apparent strain, linearity, hysteresis, temperature effects, drift, and zero shift.     

Discrete mass conservation for porous media saturated flow

Global and local mass conservation for velocity fields associated with saturated porous media flow have long been recognized as integral components of any numerical scheme attempting to simulate these flows. In this work, we study finite element discretizations for saturated porous media flow that use Taylor–Hood (TH) and Scott–Vogelius (SV) finite elements. The governing equations are modified to include a stabilization term when using the TH elements, and we provide a theoretical result that shows convergence (with respect to the stabilization parameter) to pointwise mass‐conservative solutions. We also provide results using the SV approximation pair. These elements are pointwise divergence free, leading to optimal convergence rates and numerical solutions. We give numerical results to verify our theory and a comparison with standard mixed methods for saturated flow problems. © 2013 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq 30: 625–640, 2014     

Probing Rapidly‐Ionizing Super‐Atom Molecular Orbitals in C60: A Computational and Femtosecond Photoelectron Spectroscopy Study

Super‐atom molecular orbitals (SAMOs) are diffuse hydrogen‐like orbitals defined by the shallow potential at the centre of hollow molecules such as fullerenes. The SAMO excited states differ from the Rydberg states by the significant electronic density present inside the carbon cage. We provide a detailed computational study of SAMO and Rydberg states and an experimental characterization of SAMO excited electronic states for gas‐phase C₆₀ molecules by photoelectron spectroscopy. A large band of 500 excited states was computed using time‐dependent density functional theory. We show that due to their diffuse character, the photoionization widths of the SAMO and Rydberg states are orders of magnitude larger than those of the isoenergetic non‐SAMO excited states. Moreover, in the range of kinetic energies experimentally measured, only the SAMO states photoionize significantly on the timescale of the femtosecond laser experiments. Single photon ionization of the SAMO states dominates the photoelectron spectrum for relatively low laser intensities. The computed photoelectron spectra and photoelectron angular distributions are in good agreement with the experimental results.     

Effect of Silk Protein Processing on Drug Delivery from Silk Films

Sericin removal from the core fibroin protein of silkworm silk is a critical first step in the use of silk for biomaterial‐related applications, but degumming can affect silk biomaterial properties, including molecular weight, viscosity, diffusivity and degradation behavior. Increasing the degumming time (10, 30, 60, and 90 min) decreases the average molecular weight of silk protein in solution, silk solution viscosity, and silk film glass‐transition temperature, and increases the rate of degradation of a silk film by protease. Model compounds spanning a range of physical‐chemical properties generally show an inverse relationship between degumming time and release rate through a varied degumming time silk coating. Degumming provides a useful control point to manipulate silk's material properties.

     

In-situ observation of the combustion of air-dried and wet Victorian brown coal

This work investigates the fundamental and practical implications of the application of drying technologies to Victorian brown coal combustion. The base case of 60% moisture content coal preheated prior to combustion is compared with partially dried coal (with or without pre-heating) and coal dried to equilibrium moisture content (10–15%). Pulverised coal was combusted in a drop tube furnace and in-situ observations of combustion phenomena, particle temperature and gas temperature were made. An ignition delay was found to occur when partially dried coal was combusted without pre-heating. Flame stability was also decreased when wet coal was combusted without pre-heating. No ignition delay was observed when the water in coal was heated prior to entering the furnace, as in current boilers. The peak particle temperature was found to be higher than the wall temperature by around 130 °C for dried coal, 80 °C for preheated wet coal and 40 °C for non-preheated partially dried coal. The gas temperature profile in the furnace was measured and found to lag behind the particle temperature peak. It was concluded that the evolution and evaporation of water in the wet case lead to an ignition delay, cooler peak particle temperatures and prolonged char combustion. The difference in particle temperatures between preheated wet coal and dried coal and the gas temperature behaviour was attributed to the steam gasification reaction, although studies to elucidate reasons for the differences are ongoing. The quantified results on ignition delay and particle temperatures have important implications for the design of new technologies, in particular the boilers and feed size preparation, for power generation from high-moisture brown coals.     

Cluster–surface interaction: From soft landing to implantation

The current paper presents a state-of-the-art review in the field of interaction of atomic and molecular clusters with solids. We do not attempt to overview the entire broad field, but rather concentrate on the impact phenomena: how the physics of the cluster–surface interaction depends on the kinetic energy and what effects are induced under different energetic regimes. The review starts with an introduction to the field and a short history of cluster beam development. Then fundamental physical aspects of cluster formation and the most common methods for the production of cluster beams are overviewed. For cluster–surface interactions, one of the important scenarios is the low-energy regime where the kinetic energy per atom of the accelerated cluster stays well below the binding (cohesive) energy of the cluster constituents. This case is often called soft landing: the deposition typically does not induce cluster fragmentation, i.e. the clusters tend to preserve their composition but not necessarily their shape. Specific characteristic phenomena for soft landing of clusters are summarized. They pave the way for the use of cluster beams in the formation of nanoparticle arrays with required properties for utilization in optics and electronics, as magnetic media and catalysts, in nanobiology and nanomedicine. We pay considerable attention to phenomena occurring on impact of clusters with increased kinetic energies. In particular, we discuss the physics of the intermediate regime between deposition and implantation, i.e. slight cluster embedding into the surface—otherwise known as cluster pinning. At higher impact energies, cluster structure is lost and the impact results in local damage of the surface and often in crater and hillock formation. We consider both experimental data and theoretical simulations and discuss mechanisms of these phenomena. Some analogies to the impact of macroscopic objects, e.g. meteorites are shown. This part of the paper also overviews the research on surface sputtering under high-fluence cluster beam treatment and the existing models explaining how this phenomenon can be used for efficient smoothing of surfaces on the macroscopic scale. Several examples of successful applications of the cluster beam technique for polishing of surfaces are given. We also discuss how the physical sputtering can be combined with reactive accelerated cluster erosion. The latter can be an efficient tool for dry etching of surfaces on the nanoscale. Specificity of cluster (multicomponent projectile) stopping in matter and formation of radiation damage under keV-to-MeV energy implantations are analyzed. The part about fundamental aspects of cluster implantation is followed by several examples of practical applications of keV-energy cluster ion beams. This includes ultra-shallow doping of semiconductors and formation of ultrathin insulating layers. A few examples of MeV-energy cluster implantation, leading to the formation of nanosize hillocks or pillars on the surface as well as to local phase transitions (for instance, graphite-to-diamond) are also discussed. The review is finalized by an outlook on the future development of cluster beam research.     

Gated Electron Sharing Within Dynamic Naphthalene Diimide‐Based Oligorotaxanes

The controlled self‐assembly of well‐defined and spatially ordered π‐systems has attracted considerable interest because of their potential applications in organic electronics. An important contemporary pursuit relates to the investigation of charge transport across noncovalently coupled components in a stepwise fashion. Dynamic oligorotaxanes, prepared by template‐directed methods, provide a scaffold for directing the construction of monodisperse one‐dimensional assemblies in which the functional units communicate electronically through‐space by way of π‐orbital interactions. Reported herein is a series of oligorotaxanes containing one, two, three and four naphthalene diimide (NDI) redox‐active units, which have been shown by cyclic voltammetry, and by EPR and ENDOR spectroscopies, to share electrons across the NDI stacks. Thermally driven motions between the neighboring NDI units in the oligorotaxanes influence the passage of electrons through the NDI stacks in a manner reminiscent of the conformationally gated charge transfer observed in DNA.