Enthalpy distributions and densities of states in linear polymers

Using polypropylene as an example, we applied a method we have recently developed to calculate the probability distribution of enthalpy from the temperature dependence of the heat capacity. The method involves the use of local temperature expansions of the heat capacity to calculate a set of moments of the enthalpy distribution. Using the maximum‐entropy method, one can then construct the enthalpy distribution for the system. The method is completely model free. The enthalpy distribution so obtained is the analogue of the Maxwell–Boltzmann distribution of kinetic energies for a gas, and like that function, tells one the distribution of enthalpies that an average unit in the polymer chain can have, a quantity that is crucial to understanding the chemical and physical properties of a polymer. Given the enthalpy distribution, one can then calculate the Gibbs free energy and the density of states that correspond to a particular value of enthalpy, thus giving one an expanded thermodynamics of the system in addition to the usual average quantities. We illustrate the fact that the Gibbs free‐energy distribution for this system scales as a simple function of temperature and that the density‐of ‐states function yields a simple empirical partition function for the system giving both the average thermodynamics and the distribution functions. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 1513–1518, 2001     

Demand dispersion and logistics costs in one-to-many distribution systems

When an organization decides on which groups of consumers it should target, the locations of these target consumers often play a role. Methods from the field of market segmentation are able to identify target groups with high benefit levels, but the expected costs of supplying products to the target groups are less well understood. These costs can play a large role if the locations of the customers, the demand locations, are geographically widely dispersed. This paper focuses on one-to-many distribution systems in which a central facility serves all demand points. We derive accurate logistics cost estimates from the dispersion of demand points for such systems, enabling a comparison of the expected logistics costs of different candidate target groups. The most accurate measure combines the average distance from the demand locations to a central location and the mutual distances between neighboring demand locations. The average of the distances between all pairs of locations forms a good alternative measure.     

The asymptotic estimate for the sum of two correlated classes of discounted aggregate claims with heavy tails

Consider a risk model with two correlated classes of insurance business and a constant force of interest. We assume that the correlation comes from a common shock and that the claim-size distribution is heavy-tailed. Under this setting, we investigate the tail behavior of the sum of the two correlated classes of discounted aggregate claims. We obtain the uniform asymptotic formulas for some subclass of subexponential distributions.     

Normal tracing deflectometry using a secondary light source

Scanning deflectometric profilers based on an f–gθ system are typical optical tools used to measure mirror profiles at many synchrotron facilities. Unlike these profilers, which are based on a pencil beam, here a secondary light source and a pinhole are used to construct a system that automatically selects a beam that will always pass through the pinhole and propagate along the normal direction of the measured area on the surface under test. By measuring the angle variation of the selected beam, slope variations of the surface under test can be measured. Systematic errors introduced by manufacturing defects or aberrations of an optical element, which greatly degrade the performance of traditional profilers, could be minimized by using the developed method. Simulation values of the proposed method and a conventional method are compared.     

Dimensions of branched polymers formed in simultaneous long‐chain branching and random scission

In free‐radical olefin polymerizations, the polymer‐transfer reactions could lead to chain scission as well as the formation of long‐chain branches. The Monte Carlo simulation for free‐radical polymerization that involves simultaneous long‐chain branching and random scission is used to investigate detailed branched structure. The relationship between the mean‐square radius of gyration 〈s²〉 and degree of polymerization P as well as that between the branching density and P is the same for both with and without random scission reactions—at least for smaller frequencies of scission reactions. The 〈s²〉 values were larger than those calculated from the Zimm–Stockmayer (Z‐S) equation in which random distribution of branch points is assumed, and therefore, the Z‐S equation may not be applied for low‐density polyethylenes. The elution curves of size exclusion chromatography were also simulated. The molecular weight distribution (MWD) calibrated relative to standard linear polymers is much narrower than the true MWD, and high molecular weight tails are clearly underestimated. A simplified method to estimate the true MWD from the calibrated MWD data is proposed. The MWD obtained with a light scattering photometer in which the absolute weight‐average molecular weight of polymers at each retention volume is determined directly is considered a reasonable estimate of the true MWD. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2960–2968, 2001     

Impact of average photon-energy coefficient of solar spectrum on the short circuit current of photovoltaic modules

The output energy of photovoltaic (PV) modules is influenced by the spectral irradiance distribution of the solar spectrum under outdoor conditions. To rate the precise output energy of PV modules, the correction of short circuit current (I_SC) based on actual environmental conditions is needed, because I_SC significantly depends on the shape of the spectral irradiance distribution. The average photon energy (APE) is a zero-dimensional index for spectral irradiance distribution, and APE value uniquely describes the shape of a solar spectrum. Thus, APE has an impact on I_SC of PV modules. In this contribution, the relationship between APE coefficient and I_SC of the multi-crystalline silicon, single-crystalline silicon, heterojunction intrinsic thin-layer, back contact, copper indium selenide and cadmium telluride PV modules has explored. It is revealed that APE value changes the I_SC of PV modules which appeared to have immense possibilities of I_SC correction using APE coefficient. This new approach can be very effective for precise rating the output energy of PV modules under actual outdoor conditions.     

Fast computation of Hermite normal forms of random integer matrices

This paper is about how to compute the Hermite normal form of a random integer matrix in practice. We propose significant improvements to the algorithm by Micciancio and Warinschi, and extend these techniques to the computation of the saturation of a matrix. We describe the fastest implementation for computing Hermite normal form for large matrices with large entries.     

Asymptotic exponential cones of Metzler matrices and their use in the solution of an algebraic problem

The aim of this paper is that of investigating the asymptotic exponential cone of a single Metzler matrix, introduced in [23], and of defining and analysing the new concept of asymptotic exponential cone of a family of Metzler matrices (along a certain direction). These results will provide necessary and/or sufficient conditions for the solvability of an interesting algebraic problem that arises in the context of continuous-time positive switched systems and, specifically, in the investigation of the reachability property [21,22,25].     

Detecting organic vapors using a conductometric sensor prepared from Ardel®D-100 and graphite

The composites of graphite with Ardel^?D-100 which is a trademark of a polyester of bisphenol-A with terephthalic and isophthalic acid were used as a sensing material in a conductometric vapor sensor. The magnitudes of responses are increased in the order of benzene, isobutyl acetate, isoamyl acetate, ethyl benzene and chloro benzene. This suggests that Ardel^?D-100 can be used as a sensing material for chlorobenzene, ethyl benzene and isoamyl acetate. On the other hand, specific retention volumes of the sensed vapors on Ardel^?D-100 coated on graphite were determined by inverse gas chromatography at temperatures between 200 and 260 °C. The distribution coefficient, K _s of the vapors between stationary and mobile phases in the column was obtained. It was revealed for the first time that the logarithm of K _s of the solvents varies almost linearly with their responses based on conductometric resistance of the sensing polymer composite. Subsequently, the study suggests that gas chromatographic retention data can be used in prediction of the conductometric responses of a polymeric sensor to vapors. Correspondence: Ferdane Karaman, Department of Chemistry, Yildiz Technical University, 34220 Istanbul-Esenler, Turkey     

Numerical investigation of the effects of sluice spillway roof profiles on the hydraulic characteristics

There is a need for evolving hydraulically efficient roof profile of bellmouth for high head sluice spillways, as sluice roof is susceptible to cavitation damage. In this paper, formulation and development of a numerical model for simulating the spillway flow and its application to a sluice spillway are presented. The main focus of the simulation study is to apply the developed model to investigate the effects of sluice roof profile geometry on the pressure distribution, the discharge coefficient and the nature of flow regime within the sluice bellmouth. From the analysis of results for eight different roof profiles by varying the entry and exit angles of elliptic bellmouth transition, some important observations have been suggested, which are of practical relevance to hydraulic design engineers. The numerical model results are compared for one profile with physical model study. The simulated results are in close agreement with the measured values. Copyright © 2007 John Wiley & Sons, Ltd.