Polymerization of α-Methylstyrene in p-Dioxane with Potassium as Initiator. III. Gel-Permeation Chromatographic Analyses of Polymers

Gel-permeation chromatographic studies on poly-α-methyl-styrene initiated with potassium and potassium-naphthalene in p-dioxane as solvent and polymerized at 5, 15, 25, and 40°C, have been carried out. Bimodal and trimodal distributions are observed in these polymers. It has been shown that these multimodal distributions do not arise because of the monofunctional and bifunctional living ends produced by the reaction of solvent dioxane with the living polymer. These, on the other hand, may be related to the presence of different ion-pairs which contribute to the reaction but to different extents. Contrary to the belief that only contact ion-pairs are responsible for propagation in p-dioxane because of its low dielectric constant, the presence of solvent-separated ion-pairs yielding reversible propagation has been speculated. The different components (D + A), B, and C, similar to the ones present in the a-methyl-styrene-potassium tetrahydrofuran system, have been found in the present study also and are attributed to the dead and a dormant polymer, solvent-separated ion-pair polymer, and that due to a contact pair, respectively. The extent of the formation of component (D + A) has been linked directly to the concentration of living ends. In reactions where naphthalene was used along with potassium for initiation purposes, a unique component yielding reversible propagation was observed. This has been attributed to the presence of polymer due to potassium-naphthalene complex which is different in character to a contact ion-pair but may resemble a solvent-separated ion-pair.     

Investigating the effect of nanolayered silicates on blend segmental dynamics and minor component relaxation behavior in poly(ethylene oxide)/poly(methyl methacrylate) miscible blends

Polymer–silicate nanocomposites based on poly (ethylene oxide), PEO, poly(methyl methacrylate), PMMA, and sodium montmorillonite clay were fabricated and characterized to investigate the effect of nanolayered silicates on segmental dynamics of PEO/PMMA blends. X‐ray results indicate the formation of an exfoliated morphology in the nanocomposites. At low silicate contents, an enhancement in segmental dynamics of blend nanocomposites and also PEO, minor component in blend, is observed at temperature region below blend glass transition. This result can be attributed to the improvement of the confinement effect of rigid PMMA matrix on the PEO chains by introducing a low amount of layered silicates. On the other hand, at high silicate contents, an enhancement in segmental dynamics of blend nanocomposites and PEO is observed at temperature region above blend glass transition. This behavior could be interpreted based on the reduction of monomeric friction between two polymer components, which can facilitate segmental motions of blend components in nanocomposite systems. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Infrared diffuse reflectance instrumentation and standards at NIST

A spectrophotometer system for spectral characterization of materials in the infrared has been built around a bench-top Fourier transform instrument. Its capabilities include the measurement of directional-hemispherical reflectance from 1 to 18 μm. The spectral reflectance measurement is performed with an integrating sphere with an incidence angle of 8°. Both relative and absolute measurements can be made. Several methods can be used to determine the absolute value of the directional-hemispherical reflectance of samples. The primary method used is independent of the integrating sphere theory and the requisite assumptions associated with its use. The calibration of a standard reference material (SRM) is described. This SRM has a reflectance value near 0.9 over the complete calibration range 2–18 μm. As part of the calibration procedure the spatial uniformity of the sphere throughput and the bi-directional reflectance distribution function (BRDF) of the SRM material are evaluated.     

An extended Heath–Jarrow–Morton risk-neutral drift

Using a finite dimensional Hilbert space framework, this work proposes a new derivation of the HJM [D. Heath, R. Jarrow, A. Morton, Bond pricing and the term structure of interest rates: A new methodology for contingent claims valuation, Econometrica 60 (1992) 77–105] risk-neutral drift that takes into account nonzero instantaneous correlations between factors. The results obtained generalize the original HJM risk-neutral drift and provide an approach by which interest rate derivatives can be priced using functions of directly observable factors.