Efficient approximately 2 microm Tm3+ -doped tellurite fiber laser

Laser emission in the range of 1.88-1.99 micrim from a Tm3+ -doped tellurite fiber is demonstrated when pumped with a diode-pumped Er3+/Yb3+-doped silica fiber laser operating at 1.57-1.61 microm. This pump source excites the Tm3+ ions directly into the F43 upper laser level and yields an output power of 280 mW with a slope efficiency of 76% in a 99%-12% laser cavity arrangement and a 32 cm long fiber. This result is very close to the Stokes efficiency limit of approximately 80%. This is, to the authors' knowledge, the first demonstration of high efficiency lasing in a tellurite fiber at wavelengths longer than 1.56 microm.     

Carrier-injection-based electro-optic modulator on silicon-on-insulator with a heterogeneously integrated III-V microdisk cavity

A compact electro-optic modulator on silicon-on-insulator is presented. The structure consists of a III-V microdisk cavity heterogeneously integrated on a silicon-on-insulator wire waveguide. By modulating the loss of the active layer included in the cavity through carrier injection, the power of the transmitted light at the resonant wavelength is modulated; approximately 10 dB extinction ratio and 2.73 Gbps dynamic operation are demonstrated without using any special driving techniques.     

Tm(3+)/Ho(3+) codoped tellurite fiber laser

Continuous-wave and Q-switched lasing from a Tm(3+)/Ho(3+) codoped tellurite fiber is reported. An Yb(3+)/Er(3+)-doped silica fiber laser operating at 1.6 microm was used as an in-band pump source, exciting the Tm(3+) ions into the (3)F(4) level. Energy is then nonradiatively transferred to the upper laser level, the (5)I(7) state of Ho(3+). The laser transition is from the (5)I(7) level to the (5)I(8) level, and the resulting emission is at 2.1 microm. For continuous wave operation, the slope efficiency was 62% and the threshold 0.1 W; the maximum output demonstrated was 0.16 W. Mechanical Q switching resulted in a pulse of 0.65 microJ energy and 160 ns duration at a repetition rate of 19.4 kHz.     

Interpreting technical evidence from spectral imaging of paintings by Édouard Manet in the Courtauld Gallery

The paintings by Édouard Manet in The Courtauld Gallery Déjeuner sur l'herbe (1863–68), Marguerite de Conflans en Toilette de Bal (1870–1880), Banks of the Seine at Argenteuil (1874), and A Bar at the Folies–Bergère (1882) were investigated for the first time using a range of non-invasive in situ analyses. The aims of the study were to investigate the painting techniques and materials used for this group of works and to critically evaluate the technical evidence derived from the integrated use of imaging techniques and portable spectroscopic methods in this context. The paintings were investigated by means of macro X-ray fluorescence (MA-XRF), reflection spectral imaging, portable UV–Vis–NIR spectroscopy, portable Raman spectroscopy, and reflection FTIR. MA-XRF and reflection spectral imaging allowed visualising elements in the compositions that were not visible using traditional methods of technical study. For example, MA-XRF analysis of Déjeuner sur l'herbe revealed elements of the development of the composition that provided new evidence to consider its relationship to other versions of the composition. The study also highlighted questions about the interpretation of elemental distribution maps and spectral images that did not correspond to the reworking visible in X-radiographs. For example, in A Bar at the Folies–Bergère Manet made numerous changes during painting, which were not clearly visualised with any of the techniques used. The research has wider implications for the study of Impressionist paintings, as the results will support technical studies of works by other artists of the period who used similar materials and painting methods.     

Pitfalls in the experimental recording of ultrasonic (backscatter) polar scans for material characterization

The ultrasonic polar scan (UPS), either in transmission, reflection or backscatter mode, is a promising non-destructive testing technique for the characterization of composites, providing information about the mechanical anisotropy, the viscoelastic damping, the surface roughness, and more. At present, the technique is merely being used for qualitative purposes. The limited quantitative exploration and use of the technique can be primarily ascribed to limitations of current theoretical models as well as the difficulty to perform accurate, and more importantly, reproducible UPS experiments. Over the last years, we have identified several potential pitfalls in the experimental implementation of the technique which severely deteriorate the accurateness and reproducibility of a UPS. In this paper, we make an inventory of the most important difficulties, illustrate each of them by a real experiment and present a feasible mediation, either numerical or experimental in nature. Once the experimental set-up is fine-tuned to overcome these pitfalls, it is expected that the recording of high-level UPS experiments, in combination with numerical computations, will facilitate the technique to become a fully quantitative non-destructive characterization method.     

Analysis of several subcycling schemes in partitioned simulations of a strongly coupled fluid-structure interaction

Fluid-structure interaction (FSI) simulations are used extensively to calculate the vibration of structures subjected to an internal or external flow. In the case of partitioned FSI simulations, separate flow and structure solvers are used, which requires some kind of coupling between both. The time step in both solvers is typically taken the same, but this unnecessarily leads to long calculation times when the time step is small due to stability reasons in one of the two solvers. Subcycling, the procedure where the time step of one solver is chosen smaller than the time step used in the other solver, may reduce the computational cost of the FSI simulation. The subcycling procedure can be either explicit or implicit, the latter implying the use of coupling iterations in each time step. Contrary to explicit subcycling, no stability analyses of implicit subcycling schemes are found in the literature. In this paper, the temporal stability of the implicit subcycling procedure is investigated. The one-dimensional flow in an elastic cylindrical tube is studied analytically. The results of this analysis are subsequently compared to a partitioned two-dimensional axisymmetric FSI calculation with implicit coupling between the flow and structure solvers.     

A joined theoretical-experimental investigation on the 1H and 13C NMR signatures of defects in poly(vinyl chloride)

1H and 13C chemical shifts of PVC chains have been evaluated using quantum chemistry methods in order to evidence and interpret the NMR signatures of chains bearing unsaturated and branched defects. The geometrical structures of the stable conformers have been determined using molecular mechanics and the OPLS force field and then density functional theory with the B3LYP functional and the 6-311G(d) basis set. The nuclear shielding tensor has been calculated at the coupled-perturbed Kohn-Sham level (B3LYP exchange-correlation functional) using the 6-311+G(2d,p) basis set. The computational scheme accounts for the large number of stable conformers of the PVC chains, and average chemical shifts are evaluated using the Maxwell-Boltzmann distribution. Moreover, the chemical shifts are corrected for the inherent and rather systematic errors of the method of calculation by employing linear regression equations, which have been deduced from comparing experimental and theoretical results on small alkane model compounds containing Cl atoms and/or unsaturations. For each type of defect, PVC segments presenting different tacticities have been considered because it is known from linear PVC chains that the racemic (meso) dyads are characterized by larger (smaller) chemical shifts. NMR signatures of unsaturations in PVC chains have been highlighted for the internal -CH=CH- and -CH=CCl- units as well as for terminal unsaturations like the chloroallylic -CH=CH-CH2Cl group. In particular, the 13C chemical shifts of the two sp2 C atoms are very close for the chloroallylic end group. The CH2 and CHCl units surrounding an unsaturation present also specific 13C chemical shifts, which allow distinguishing them from the others. In the case of the proton, the CH2 unit of the -CHCl-CH2-CCl=CH- segment presents a larger chemical shift (2.6-2.7 ppm), while some CHCl units close to the -CH=CH- unsaturations appear at rather small chemical shifts (3.7 ppm). The -CH2Cl and -CHCl-CH2Cl branches also display specific signatures, which result in large part from modifications of the equilibrium conformations and their reduced number owing to the increased steric interactions. These branches lead to the appearance of 13C peaks at lower field associated either to the CH unit linking the -CH2Cl and -CHCl-CH2Cl branches (50 ppm) or to the CHCl unit of the ethyl branches (60 ppm). The corresponding protons resonate also at specific frequencies: 3.5-4.0 ppm for the -CH2Cl branch or 3.8-4.2 ppm for the terminal unit of the -CHCl-CH2Cl branch. Several of these signatures have been detected in the experimental 1H and 13C NMR spectra and are consistent with the reaction mechanisms.     

Capillary adhesion in the limit of saturation: thermodynamics, self-consistent field modeling and experiment

We introduce a simple thermodynamic argument for capillary adhesion forces, for various geometries, in the limit of saturation of the bulk phase. For one specific geometry (i.e., the sphere-plate geometry such as that found in the colloidal probe AFM technique), we provide evidence of the validity of our model by comparison with experiment and self-consistent field calculations. With this latter numerical technique, we also discuss deviations from the macroscopic argument both when the system is moved away from saturation and when the capillary bridge becomes so small that macroscopic thermodynamics is no longer accurate.     

A novel Ni(4) complex exhibiting microsecond quantum tunneling of the magnetization

A highly asymmetric Ni(II) cluster [Ni(4)(OH)(OMe)(3)(Hphpz)(4)(MeOH)(3)](MeOH) (1) (H(2)phpz=3-methyl-5-(2-hydroxyphenyl)pyrazole) has been prepared and its structure determined by means of single-crystal X-ray diffraction by using synchrotron radiation. Variable-temperature bulk-magnetization measurements show that the complex exhibits intramolecular-ferromagnetic interactions leading to a spin ground state S=4 with close-lying excited states. Magnetization and high-frequency EPR measurements suggest the presence of sizable Ising-type magnetic anisotropy, with zero-field splitting parameters D=-0.263 cm(-1) and E=0.04 cm(-1) for the spin ground state, and an isotropic g value of 2.25. The presence of both axial and transverse anisotropy was confirmed through low-temperature specific heat determinations down to 300 mK, but no slow relaxation of the magnetization was observed by AC measurements down to 1.8 K. Interestingly, AC susceptibility measurements down to temperatures as low as 23 mK showed no indication of slow relaxation of the magnetization in 1. Thus, despite the presence of an anisotropy barrier (U approximately 4.21 cm(-1) for the purely axial limit), the magnetization relaxation remains extremely fast down to the lowest temperatures. The estimated quantum tunneling rate, Gamma>0.667 MHz, makes this complex a prime candidate for observation of coherent tunneling of the magnetization.     

Electrochemistry and Spin-Crossover Behavior of Fluorinated Terpyridine-Based Co(II) and Fe(II) Complexes

Due to their ability to form stable molecular complexes that have tailor-made properties, terpyridine ligands are of great interest in chemistry and material science. In this regard, we prepared two terpyridine ligands with two different fluorinated phenyl rings on the backbone. The corresponding Co^II and Fe^II complexes were synthesized and characterized by single-crystal X-ray structural analysis, electrochemistry and temperature-dependent SQUID magnetometry. Single crystal X-ray diffraction analyses at 100 K of these complexes revealed Co−N and Fe−N bond lengths that are typical of low spin Co^II and Fe^II centers. The metal centers are coordinated in an octahedral fashion and the fluorinated phenyl rings on the backbone are twisted out of the plane of the terpyridine unit. The complexes were investigated with cyclic voltammetry and UV/Vis-NIR spectroelectrochemistry. All complexes show a reversible oxidation and several reduction processes. Temperature dependent SQUID magnetometry revealed a gradual thermal SCO behavior in two of the complexes, while EPR spectroscopy provided further insights on the electronic structure of the metal complexes, as well as site of reduction.