Mid-IR real-time monitoring of the carbocationic polymerization of isobutylene and styrene

The in-situ monitoring of the living carbocationic polymerization of isobutylene (IB) and styrene (St) with a fiber optic Attenuated Total Reflection (ATR) probe in the mid-IR "fingerprint" range is reported here for the first time. Monomer consumption was followed by the disappearance of the C=C stretching for both IB and St, and the C−H bending of the CH₃-group in IB. The formation of polyisobutylene (PIB) was also monitored by tracing the asymmetrical doublet characteristic of C−H bending of the t-butyl groups of the PIB. Conversion measurements by conventional off-line gravimetry correlated well with the new technique. Received: 27 August 1997/Revised version: 2 November 1997/Accepted: 20 November 1997     

Optical acceptance function of modified compound parabolic concentrators with linear corrugated reflectors

For reflective cylindrical concentrators the acceptance function, as determined in the meridian plane, remains constant for more oblique planes of incidence. However, if the reflective surface has a linear corrugated structure, it is possible to increase the acceptance in the meridian plane at the expense of reduced acceptance at a more oblique incidence. A ray-tracing study has been performed on the optical properties of troughlike compound parabolic concentrators (CPC's) with linear corrugated reflectors. Calculations of angular acceptance for a modified CPC with concentration C = x is presented. A possible application of this new concentrator is as a secondary concentrator for tracking parabolic troughs.     

New aspects of transversal1H-NMR relaxation in natural rubber vulcanizates

Summary Structure and dynamics of unfilled and carbon black filled natural rubber vulcanizates were investigated by means of transversal¹H-NMR-relaxation. A simple theoretical model including different motions in polymer network was extended by the discussion of an anisotropy parameter of segmental motion not only for the intercrosslink chains but also for the dangling ends. It makes characterization of the filling state of the network possible to approximate. The effect of increasing correlation times _f of the fast anisotropic local motion with reduction of the molecular mass of intercrosslink chains which was observed, but not cleared up in previous investigation is evidently smaller by using this modified model in accordance with the expectation of a local motion. The determined values of M_c are in good agreement with the results of fits by using the unmodified relaxation function.¹³C-NMR-spectra and stress-strain-experiments are leading in most cases to similar results, especially for M_c.     

Russian doll type cryogenic traps: improved design and isotope separation effects

An improved cryogenic trap for removing micromole quantities of condensables from gas mixtures is described. It is based on the so-called Russian doll design, with which extraordinary trapping efficiencies at flow rates of up to 10 L/min are obtained. The active element consists of one or more nested glass fiber thimbles. Despite the large fiber area, quantitative retrieval of condensed CO(2) is obtained. The new design is demountable and incorporates a heat exchange section; trapping efficiency depends little on the level of coolant, as has been tested for CO(2). When fractionation is induced by incomplete trapping, a small isotopic enrichment in (13)C occurs. It also has been discovered that when He is used as carrier gas, a gas chromatographic effect for CO occurs in Russian doll traps, accompanied by a large isotope separation, in which the elution sequence corresponds to the vapor pressure ratios of the isotopomers.     

Stability under vacuum of silicon trap detectors and their use as transfer instruments in cryogenic radiometry

The stability of the responsivity of trap detectors under vacuum has been studied by means of a special chamber designed for the test of photodetectors at low pressure. The first experiments at a wavelength of 647 nm show that the responsivity variations are smaller than the uncertainties of the measurements, approximately 3 parts in 10(5), when the detector operates successively in air, under vacuum, and then again in air. Calculations based on experiments with single windowless photodiodes indicate that the change in trap responsivity that is due to vacuum effects should be smaller than 1 part in 10(5), at least in the visible part of the wavelength range. This stability makes trap detectors suitable for cryogenic radiometry when one uses transfer detectors under vacuum.     

Range of validity of the Rayleigh-Debye-Gans theory for optics of fractal aggregates

The range of validity of the Rayleigh-Debye-Gans approximation for the optical cross sections of fractal aggregates (RDG-FA) that are formed by uniform small particles was evaluated in comparison with the integral equation formulation for scattering (IEFS), which accounts for the effects of multiple scattering and self-interaction. Numerical simulations were performed to create aggregates that exhibit mass fractallike characteristics with a wide range of particle and aggregate sizes and morphologies, including x(p) = 0.01-1.0, ‖m - 1‖ = 0.1-2.0, N = 16-256, and D(f) = 1.0-3.0. The percent differences between both scattering theories were presented as error contour charts in the ‖m - 1‖x(p) domains for various size aggregates, emphasizing fractal properties representative of diffusion-limited cluster-cluster aggregation. These charts conveniently identified the regions in which the differences were less than 10%, between 10% and 30%, and more than 30% for easy to use general guidelines for suitability of the RDG-FA theory in any scattering applications of interest, such as laser-based particulate diagnostics. Various types of aggregate geometry ranging from straight chains (D(f) ≈ 1.0) to compact clusters (D(f) ≈ 3.0) were also considered for generalization of the findings. For the present computational conditions, the RDG-FA theory yielded accurate predictions to within 10% for ‖m - 1‖ to approximately 1 or more as long as the primary particles in aggregates were within the Rayleigh scattering limit (x(p) ≤ 0.3). Additionally, the effect of fractal dimension on the performance of the RDG-FA was generally found to be insignificant. The results suggested that the RDG-FA theory is a reasonable approximation for optics of a wide range of fractal aggregates, considerably extending its domain of applicability.     

Visual comparability of 3D regular sampling and reconstruction

The Body-Centered Cubic (BCC) and Face-Centered Cubic (FCC) lattices have been analytically shown to be more efficient sampling lattices than the traditional Cartesian Cubic (CC) lattice, but there has been no estimate of their visual comparability. Two perceptual studies (each with N = 12 participants) compared the visual quality of images rendered from BCC and FCC lattices to images rendered from the CC lattice. Images were generated from two signals: the commonly used Marschner-Lobb synthetic function and a computed tomography scan of a fish tail. Observers found that BCC and FCC could produce images of comparable visual quality to CC, using 30-35 percent fewer samples. For the images used in our studies, the L(2) error metric shows high correlation with the judgement of human observers. Using the L(2) metric as a proxy, the results of the experiments appear to extend across a wide range of images and parameter choices.     

Adaptive isogeometric analysis by local h-refinement with T-splines

Isogeometric analysis based on non-uniform rational B-splines (NURBS) as basis functions preserves the exact geometry but suffers from the drawback of a rectangular grid of control points in the parameter space, which renders a purely local refinement impossible. This paper demonstrates how this difficulty can be overcome by using T-splines instead. T-splines allow the introduction of so-called T-junctions, which are related to hanging nodes in the standard FEM. Obeying a few straightforward rules, rectangular patches in the parameter space of the T-splines can be subdivided and thus a local refinement becomes feasible while still preserving the exact geometry. Furthermore, it is shown how state-of-the-art a posteriori error estimation techniques can be combined with refinement by T-splines. Numerical examples underline the potential of isogeometric analysis with T-splines and give hints for further developments.