Thermodynamics of polystyrene solutions. I. Interaction parameters and polymer order

The Maron theory was used to deduce from mostly osmotic pressure and light-scattering data the interaction parameters as a function of concentration, temperature, and polymer molecular weight for solutions of polystyrene in seven different solvents. These interaction parameters were then utilized to calculate the activity coefficients of the solvent in more concentrated solutions for comparison with experimental values deduced from vapor pressure measurements. When order was absent in the polymers (all cases but two), the agreement between calculated and observed activity coefficients was found to be very good. In the two cases where order was present, the activity coefficients observed in the concentrated solutions were higher than those calculated. These deviations were employed to find the degree of polymer order both in solution and in the original polymers.     

Thermodynamics of poly(α-olefin) solutions

The Maron theory of polymer solutions was used to examine the 30°C vapor pressure data of Tait and Livesey on solutions of polyheptene-1, polydecene-1, polydodecene-1, and polyoctadecene-1 in toluene. For polyheptene-1 and polydecene-1, excellent agreement was obtained between theory and experiment over the entire concentration range studied. However, for the other two polymers, deviations were observed between the calculated and observed vapor pressures at higher solution concentrations. These deviations were used to show the presence of crystallinity in these and to ascertain the amounts. Further, it was shown that only one crystalline form of the polymer was present in the polydodecene-1, whereas in the polyoctadecene-1 two crystalline forms were detected. These observations, confirmed by measurements with a differential thermal analyzer (DTA), indicate that for polydodecene-1 and one of the crystalline forms in polyoctadecene-1 the crystallization involves alignment of both backbone and side chains; however, the lower melting form in polyoctadecene-1 appears to have only the side chains aligned in the crystal lattice.     

Long run behaviour of the autocovariance function of ARCH(∞) models

The asymptotic properties of the memory structure of ARCH($\infty$) equations are investigated. This asymptotic analysis is achieved by expressing the autocovariance function of ARCH($\infty$) equations as the solution of a linear Volterra summation equation and analysing the properties of an associated resolvent equation via the admissibility theory of linear Volterra operators. It is shown that the autocovariance function decays subexponentially (or geometrically) if and only if the kernel of the resolvent equation has the same decay property. It is also shown that upper subexponential bounds on the autocovariance function result if and only if similar bounds apply to the kernel.     

Search for Neutrinoless Double-Beta Decay in ^{136}Xe with EXO-200

We report on a search for neutrinoless double-beta decay of ^{136}Xe with EXO-200. No signal is observed for an exposure of 32.5?kg?yr, with a background of ～1.5×10^{-3} kg^{-1}?yr^{-1}?keV^{-1} in the ±1σ region of interest. This sets a lower limit on the half-life of the neutrinoless double-beta decay T_{1/2}^{0νββ}(^{136}Xe)>1.6×10^{25} yr (90% C.L.), corresponding to effective Majorana masses of less than 140-380?meV, depending on the matrix element calculation.     

High‐energy X‐ray diffraction using the Pixium 4700 flat‐panel detector

The Pixium 4700 detector represents a significant step forward in detector technology for high‐energy X‐ray diffraction. The detector design is based on digital flat‐panel technology, combining an amorphous Si panel with a CsI scintillator. The detector has a useful pixel array of 1910 × 2480 pixels with a pixel size of 154 µm × 154 µm, and thus it covers an effective area of 294 mm × 379 mm. Designed for medical imaging, the detector has good efficiency at high X‐ray energies. Furthermore, it is capable of acquiring sequences of images at 7.5 frames per second in full image mode, and up to 60 frames per second in binned region of interest modes. Here, the basic properties of this detector applied to high‐energy X‐ray diffraction are presented. Quantitative comparisons with a widespread high‐energy detector, the MAR345 image plate scanner, are shown. Other properties of the Pixium 4700 detector, including a narrow point‐spread function and distortion‐free image, allows for the acquisition of high‐quality diffraction data at high X‐ray energies. In addition, high frame rates and shutterless operation open new experimental possibilities. Also provided are the necessary data for the correction of images collected using the Pixium 4700 for diffraction purposes.     

Modeling covariance matrices via partial autocorrelations

We study the role of partial autocorrelations in the reparameterization and parsimonious modeling of a covariance matrix. The work is motivated by and tries to mimic the phenomenal success of the partial autocorrelations function (PACF) in model formulation, removing the positive-definiteness constraint on the autocorrelation function of a stationary time series and in reparameterizing the stationarity-invertibility domain of ARMA models. It turns out that once an order is fixed among the variables of a general random vector, then the above properties continue to hold and follow from establishing a one-to-one correspondence between a correlation matrix and its associated matrix of partial autocorrelations. Connections between the latter and the parameters of the modified Cholesky decomposition of a covariance matrix are discussed. Graphical tools similar to partial correlograms for model formulation and various priors based on the partial autocorrelations are proposed. We develop frequentist/Bayesian procedures for modelling correlation matrices, illustrate them using a real dataset, and explore their properties via simulations.     

Facile Synthesis of Pentacarbonyltungsten(0) Complexes with Oxaphosphirane Ligands

Facile synthesis of tungsten(0) complexes of the type 7a – g (R¹ = C₅Me₅) and 8a – g (R¹ = CH(SiMe₃)₂) using transient Li/Cl phosphanylidenoid tungsten(0) complexes 4 , 5 and carbonyl derivatives 6a – g is reported; furthermore, for all complexes NMR, IR spectroscopic, mass spectrometric investigations and, in addition, single‐crystal X‐ray structures of complexes 7b , d – g and 8b , d are presented.     

Temperature effects on retention and efficiency of butyl and lauryl acrylate porous polymer monoliths in capillary electrochromatography

The development of organic porous polymer monoliths represents an alternative approach to stationary phase design. The use of these materials has helped to rekindle interest in capillary electrochromatography. Although a large number of investigations have explored different monolith recipes, polymerization conditions, and application challenges, few investigations have addressed the fundamentals of this separation mode with this type of material. This study addresses the thermodynamics of the reversed phase retention mechanism on 100% butyl acrylate and 1:3 butyl:lauryl acrylate (volume/volume ratio) porous polymer monoliths used in a capillary electrochromatography mode. Linear van't Hoff plots yield enthalpies of retention of ?3.9 to ?14.3 kJ/mol on two different, but related columns for five selected hydrophobic analytes across a thirty degree temperature range. Minimum plate heights were only moderately impacted over this temperature range.     

Local canted spin behaviour in Co1.4−x Zn x Ge0.4Fe1.2O4 spinels: A macroscopic, mesoscopic and microscopic study

DC magnetization, neutron depolarization and neutron diffraction (with both polarized and unpolarized neutrons) measurements have been reported for the Co_1.1−x Zn _x Ge_0.1Fe_1.2O₁ spinels with x=0.5, 0.6 and 0.7. Neutron depolarization and neutron diffraction measurements confirm the presence of a long range ferrimagnetic ordering of the local canted spins in these ferrite samples. The observed features of low field magnetization have been explained under the framework of thermally activated domain wall movement of ferrimagnetic arrangement of local canted spins. An important role of magnetic anisotropy (due to the presence of Co²⁺ ions) in establishing the magnetic ordering and domain kinetics in these ferrites has been observed.