Ion dynamics and sublattice melting in the superionic conductor PbF2

The F¹⁹ relaxation rates in PbF₂ exhibit anamolous changes as the temperature is increased into the superionic phase. These changes confirm the concept of a continuous melting of the fluorine sublattice and show that the fluorine motion in the superionic phase is highly correlated.     

Surface chemistry and diffusion of trace and alloying elements during in vacuum thermal deoxidation of stainless steel

Removal of the native surface oxide from steel is an important initial step during vacuum brazing. Trace and alloying elements in steel, such as Mn, Si, and Ni, can diffuse to the surface and influence the deoxidation process. The detailed surface chemical composition and grain morphology of the common stainless-steel grade 316L is imaged and spectroscopically analyzed at several stages of in-vacuum annealing from room temperature up to 850°C. Measurements are performed using synchrotron-based X-ray photoemission and low-energy electron microscopy (XPEEM/LEEM). The initial native Cr surface oxide is amorphous and unaffected by the underlying Fe grain morphology. After annealing to ~700°C, the grain morphology is seen at the surface, persisting also after the complete oxygen removal at 850°C. The surface concentration of first Mn and then Si increases significantly when annealing to 500°C and 700°C, respectively, while Ni and Cr concentrations do not change. Mn and Si are not located only in grain boundaries or clusters but are distributed across over the surface. Both Mn and Si appear as oxides, while Cr oxide becomes metallic Cr. Annealing from 500°C up to 850°C leads to the removal of first the Mn and then Si oxides from the surface, while Cr and Fe are completely reduced to metals. Deoxidation of Cr occurs faster at the grain boundaries, and the final Cr metal surface content varies between the grains. The findings are summarized in a general qualitative model, relevant for austenite steels.     

Enzyme activity measurement via spectral evolution profiling and PARAFAC

The recent advances in multi-way analysis provide new solutions to traditional enzyme activity assessment. In the present study enzyme activity has been determined by monitoring spectral changes of substrates and products in real time. The method relies on measurement of distinct spectral fingerprints of the reaction mixture at specific time points during the course of the whole enzyme catalyzed reaction and employs multi-way analysis to detect the spectral changes. The methodology is demonstrated by spectral evolution profiling of Fourier Transform Infrared (FTIR) spectral fingerprints using parallel factor analysis (PARAFAC) for pectin lyase, glucose oxidase, and a cellulase preparation.     

Mechanical and structural properties of native and alkali-treated bacterial cellulose produced by Gluconacetobacter xylinus strain ATCC 53524

Mechanical properties of hydrated bacterial cellulose have been tested as a function of fermentation time and following the alkali treatment required for sterilisation prior to biomedical applications. Bacterial cellulose behaves as a viscoelastic material, with brittle failure reached at approximately 20% strain and 1.5 MPa stress under uniaxial tension. Treatment with 0.1 M NaOH resulted in minimal effects on the mechanical properties of bacterial cellulose. Fermentation time had a large effect on both bacterial numbers and cellulose yield but only minor effects on mechanical properties, showing that the fermentation system is a robust method for producing cellulose with predictable materials properties. The failure zone in uniaxial tension was shown to be associated with large-scale fibre alignment, consistent with this being the major determinant of mechanical properties. Under uniaxial tension, elastic moduli and failure stresses are an order of magnitude lower than those obtained under biaxial tension, consistent with the fibre alignment mechanism which is not available under biaxial tension.     

Nafion Coated Silver Amalgam Electrode for Determination of Trace Metals by Anodic Stripping Voltammetry

This paper describes characterization and application of Nafion coated solid silver amalgam electrodes to prevent surface fouling of surfactants in determination of trace metals by differential pulse anodic stripping voltammetry (DPASV). Polymer films of different thickness were tested using Nafion solutions in the range 0.25%–1%. Optimum thickness was archived using a 0.5% Nafion solution, resulting in both increased response and stability over time compared to uncoated electrodes. The influence of model surface active macromolecules was studied using triton X‐100, sodium dodecyl sulfate, dodecyl pyridinium chloride and bovine serum albumin as representatives for surfactants. The resistance to surfactants makes the studied Nafion coated solid silver amalgam electrodes an interesting alternative for practical use in environmental monitoring.     

Finite element implementation and numerical issues of strain gradient plasticity with application to metal matrix composites

A framework of finite element equations for strain gradient plasticity is presented. The theoretical framework requires plastic strain degrees of freedom in addition to displacements and a plane strain version is implemented into a commercial finite element code. A couple of different elements of quadrilateral type are examined and a few numerical issues are addressed related to these elements as well as to strain gradient plasticity theories in general. Numerical results are presented for an idealized cell model of a metal matrix composite under shear loading. It is shown that strengthening due to fiber size is captured but strengthening due to fiber shape is not. A few modelling aspects of this problem are discussed as well. An analytic solution is also presented which illustrates similarities to other theories.     

Hybrid density functional theory/molecular mechanics calculations of two-photon absorption of dimethylamino nitro stilbene in solution

The dimethylamino nitro stilbene (DANS) molecule is studied for exploring solvent effects on two-photon absorption using the quantum mechanical/molecular mechanical (QM/MM) response theory approach, where the quantum part is represented by density functional theory. We have explored the role of geometrical change of the chromophore in solution, the importance of taking a dynamical average over the sampled structures and the role of a granular representation of the polarization and electrostatic interactions with the classically described medium. The line shape function was simulated by the QM/MM technique thereby allowing for non-empirical prediction of the absolute two-photon cross section. We report a maximum in the TPA cross section for a medium of intermediate solvent polarity (i.e. in chloroform) and provide the grounds for an explanation of this effect which recently has been experimentally observed for a series of charge transfer species in solvents of different polarity. The calculations of absorption energies reproduce well the positive solvatochromic behavior of DANS and are in good agreement with experimental spectra available for the chloroform and DMSO solvents. In line with recent development of the QM/MM response technique for color modeling, we find this methodology to offer a versatile tool to predict and analyze two-photon absorption phenomena taking place within a medium.     

Local density of states and interface effects in semimetallic ErAs nanoparticles embedded in GaAs

The atomic and electronic structures of ErAs nanoparticles embedded within a GaAs matrix are examined via cross-sectional scanning tunneling microscopy and spectroscopy (XSTM/XSTS). The local density of states (LDOS) exhibits a finite minimum at the Fermi level demonstrating that the nanoparticles remain semimetallic despite the predictions of previous models of quantum confinement in ErAs. We also use XSTS to measure changes in the LDOS across the ErAs/GaAs interface and propose that the interface atomic structure results in electronic states that prevent the opening of a band gap.     

Suppression of electron temperature gradient turbulence via negative magnetic shear in NSTX

Negative magnetic shear is found to suppress electron turbulence and improve electron thermal transport for plasmas in the National Spherical Torus Experiment (NSTX). Sufficiently negative magnetic shear results in a transition out of a stiff profile regime. Density fluctuation measurements from high-k microwave scattering are verified to be the electron temperature gradient (ETG) mode by matching measured rest frequency and linear growth rate to gyrokinetic calculations. Fluctuation suppression under negligible E×B shear conditions confirm that negative magnetic shear alone is sufficient for ETG suppression. Measured electron temperature gradients can significantly exceed ETG critical gradients with ETG mode activity reduced to intermittent bursts, while electron thermal diffusivity improves to below 0.1?electron gyro-Bohms.