Ultrasonic spectroscopic evaluation of the ring‐opening metathesis polymerization of dicyclopentadiene

An in situ ultrasonic spectroscopy technique was used to study the ring‐opening metathesis polymerization of dicyclopentadiene catalyzed by bis(tricyclohexylphosphine)benzylidene ruthenium dichloride. A reaction cell employing a flexible poly(ethylene terephthalate) window for pulse echo ultrasonic spectroscopy was used to monitor the polymerization. The changes in the density, wave speed, acoustic modulus, and attenuation were all simultaneously monitored. In comparison with Fourier transform infrared (FTIR) spectroscopy data, the changes in the density, velocity, and modulus only accurately measured the rate constant for the metathesis of the cyclopentyl unsaturation. The ultrasonic values were within 6% of the values determined by FTIR. The activation energy for metathesis of the cyclopentyl unsaturation was 84 kJ mol^?1, following first‐order kinetics. Rate constants for the polymerization of the norbornyl unsaturation could not be determined by ultrasound. The gel point, vitrification, and qualitative information about the reaction rate could be determined from the change in the attenuation. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1323–1333, 2003     

Application of a generalized residual model to frequency domain modal parameter estimation

Residuals have long been used in frequency domain parameter estimation methods to model the influence of out-of-band modes but, typically, as a fixed set of no more than two or three terms. Recently, a systematic approach to the use of residual polynomials has led to the development of a generalized residual model. The use of a generalized residual model with rational fraction polynomial frequency domain parameter estimation methods allows the contribution of out-of-band modes to be included without increasing the model order and creating additional computational poles. Of particular interest is the use of the generalized residual for single-degree-of-freedom (s.d.o.f.) techniques, which generally do not consider the residual effects and suffer accordingly. With the use of generalized residuals, it becomes possible to properly account for nearby modes and also extract accurate residues with an s.d.o.f. algorithm. The development of the generalized residual polynomial model is outlined and a new s.d.o.f. frequency domain algorithm with generalized residuals is developed.     

Mechanisms of n‐butanol formation in butyl acrylate latexes

The mechanisms involved in the formation of n‐butanol during the synthesis of butyl acrylate containing latices were investigated. The experimental results showed that neither the hydrolysis of butyl acrylate nor of the ester bond in the butyl acrylate segments of the polymer played a major role in the formation of n‐butanol, which was mainly generated from the polymer backbone, by transfer reactions to polymer chain followed by cyclization. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5838–5846, 2007     

Multi-mode wave propagation in ribbed plates: Part I,wavenumber-space characteristics

This paper addresses the issue of energy propagation features in ribbed panels over a wide frequency range. First, a tool for estimating the wave propagation characteristics of one- and two-dimensional structures by k-space analysis is presented. This tool uses a concept of Inhomogeneous Wave Correlation with sparse measured or extracted data, and leads to the estimation of θ-dependent wavenumbers. Here, the method is employed with the sparse simulated and measured normal velocities of a set of ribbed panels and new insights into their k-space behavior are highlighted. Behavior is essentially characterized at low frequencies by structural orthotropy. Comparisons with homogenized data show very good agreement. At higher frequencies, a new behavior pattern is observed and explained both numerically and experimentally. This is a multi-modal waveguide type of propagation in a direction parallel to the ribs.     

Buckling of a stiff thin film on a compliant substrate in large deformation

A finite-deformation theory is developed to study the mechanics of thin buckled films on compliant substrates. Perturbation analysis is performed for this highly nonlinear system to obtain the analytical solution. The results agree well with experiments and finite element analysis in wavelength and amplitude. In particular, it is found that the wavelength depends on the strain. Based on the accurate wavelength and amplitude, the membrane and peak strains in thin films, and stretchability and compressibility of the system are also obtained analytically.     

Multi-layer thin films/substrate system subjected to non-uniform misfit strains

Current methodologies used for the inference of thin film stress through curvature measurement are strictly restricted to stress and curvature states that are assumed to remain uniform over the entire film/substrate system. These methodologies have recently been extended to a single layer of thin film deposited on a substrate subjected to the non-uniform misfit strain in the thin film. Such methodologies are further extended to multi-layer thin films deposited on a substrate in the present study. Each thin film may have its own non-uniform misfit strain. We derive relations between the stresses in each thin film and the change of system curvatures due to the deposition of each thin film. The interface shear stresses between the adjacent films and between the thin film and the substrate are also obtained from the system curvatures. This provides the basis for the experimental determination of thin film stresses in multi-layer thin films on a substrate.     

Adaptive server staffing in the presence of time-varying arrivals: a feed-forward control approach

We study the short-term staffing problem of systems that experience random, non-stationary demand. The typical method to accommodate changes in arrival rate is to use historical data to identify peak periods and associated forecasting for upcoming time windows. In this paper, we develop a method that instead detects change as it happens. Motivated by an automatic call distributor system in a call centre with time-varying arrivals, we propose a change detection algorithm based upon non-homogeneous Poisson processes. The proposed method is general and may be thought of as a feed-forward strategy, in which we detect a change in the arrival process, estimate the new magnitude of the arrival rate, and assign an appropriate number of servers to the tasks. The generalized likelihood ratio statistic is used and a recommendation for its decision limit is developed. Simulation results are used to evaluate the performance of the detector in the context of a telephone call centre.     

Closed-form solutions for a rectangular layer with central crack under anti-plane shear stress

We consider the problem of determining the stress distributionin a finite rectangular elastic layer containing a Griffithcrack which is opened by internal shear stress acting alongthe length of the crack. The mode III crack is assumed to belocated in the middle plane of the rectangular layer. The followingtwo problems are considered: (A) the central crack is perpendicularto the two fixed lateral surfaces and parallel to the othertwo stress-free surfaces; (B) all the lateral surfaces of therectangular layer are clamped and the central crack is parallelto the two lateral surfaces. By using Fourier transformations,we reduce the solution of each problem to the solution of dualintegral equations with sine kernels and a weight function whichare solved exactly. Finally, we derive closed-form expressionsfor the stress intensity factor at the tip of the crack andthe numerical values for the stress intensity factor at theedges of the cracks are presented in the form of tables.     

Combined supercritical-fluid chromatography/mass spectrometry in the analysis of diuron in plasma using on-line phase-system switching

On-line sample pretreatment by means of the phase-system switching approach is an interesting technique for the analysis of aqueous samples, e.g., plasma, by means of supercritical-fluid chromatography. In order to analyse plasma samples the following analytical procedure is used. The plasma sample is injected on to a short precolumn, which is washed with water and subsequently dried with nitrogen. Next, the solutes are desorbed with the supercritical mobile phase, analysed with packed-column supercritical-fluid chromatography and detected with either a UV detector or a mass spectrometer, equipped with a moving-belt interface. The herbicide diuron is selected as a test compound to study the feasibility of this approach. Using a selective detector the procedure is sufficiently sensitive to detect diuron in plasma, but not appropriate to detect the diuron metabolites in a post-mortem plasma sample. These have been identified with liquid chromatography/mass spectrometry. The detection limit of diuron in plasma using the procedure described is about 30 ng/mL.