Physical aging of a polyetherimide: Creep and DSC measurements

Creep and differential scanning calorimetry (DSC) measurements have been used to study the physical aging behavior of a polyetherimide. Isothermal aging temperatures ranged from 160°C to T_g with aging times ranging from 10 min to 8 days. The only measurable effect of physical aging on the short-time creep curves is a shift of the creep compliance to longer times. Andrade plots of the compliance versus the cube root of time are linear at short times with the slope β decreasing with increasing aging time to a constant value once equilibrium is reached. Log β³ is related directly to the degree to which the creep curves shift to longer times with physical aging, and is used in this work as a measure of physical aging. A reduced curve of log β³ versus log aging time is obtained for the aging temperatures investigated by appropriate vertical and horizontal shifts. The enthalpy change during aging increases linearly with the logarithm of the aging time, t_a, leveling off at equilibrium at values which increase with decreasing aging temperature. Hence, both nonequilibrium and equilibrium temperature shift factors can be calculated from the DSC data. Good agreement is observed between the equilibrium temperature shift factors obtained from the creep and DSC data. The temperature dependence of the nonequilibrium temperature shift factors is found to be an order of magnitude smaller than that of the equilibrium shift factors. The time scales to reach equilibrium for enthalpy and for mechanical measurements are found to be the same within experimental error. © 1995 John Wiley & Sons, Inc.     

Optimality conditions and duality theory for minimizing sums of the largest eigenvalues of symmetric matrices

The sum of the largest eigenvalues of a symmetric matrix is a nonsmooth convex function of the matrix elements. Max characterizations for this sum are established, giving a concise characterization of the subdifferential in terms of a dual matrix. This leads to a very useful characterization of the generalized gradient of the following convex composite function: the sum of the largest eigenvalues of a smooth symmetric matrix-valued function of a set of real parameters. The dual matrix provides the information required to either verify first-order optimality conditions at a point or to generate a descent direction for the eigenvalue sum from that point, splitting a multiple eigenvalue if necessary. Connections with the classical literature on sums of eigenvalues and eigenvalue perturbation theory are discussed. Sums of the largest eigenvalues in the absolute value sense are also addressed.This paper is dedicated to Phil Wolfe on the occasion of his 65th birthday.The work of this author was supported by the National Science Foundation under grants CCR-8802408 and CCR-9101640.The work of this author was supported in part during a visit to Argonne National Laboratory by the Applied Mathematical Sciences subprogram of the Office of Energy Research of the U.S. Department of Energy under contract W-31-109-Eng-38, and in part during a visit to the Courant Institute by the U.S. Department of Energy under Contract DEFG0288ER25053.     

On complementability of certain generalized hypercenters in Artinian modules

We prove that, in an Artinian module, the upper FC-hypercenter over an infinite FC-hypercentral locally solvable group has a direct complement. Thus, we obtain a generalization of one of Zaitsev’s theorems and one of Duan’s theorems.     

Band bending at the Si(1 1 1)–SiO2 interface induced by low-energy ion bombardment

Experiments employing photoreflectance spectroscopy have uncovered band bending due to electrically active defects at the Si(1 1 1)–SiO₂ interface after sub-keV Ar⁺ ion bombardment. The band bending of about 0.5 eV resembles that for Si(1 0 0)–SiO₂, and both interfaces exhibit two kinetic regimes for the evolution of band bending upon annealing due to defects healing. The healing takes place about an order of magnitude more quickly at the (1 1 1) interface, however, probably because of less fully saturated bonding and higher compressive stress.     

Feasibility Exploration of Laser‐based Techniques for Characterization of a Flashing Jet

Two‐phase flows hold an interest in many areas of science and engineering. In the safety field, one such topic is the accidental release of flammable and toxic pressure‐liquefied gases. In case of such a release, a flashing vapor explosion takes place resulting in a very dense two‐phase cloud. If the released substance is flammable, this cloud can be combustible and can lead to deflagration or detonation. For understanding the source processes of flashing and risk assessment, data related to cloud characteristics (i.e. droplet size, velocity etc.) is needed especially in the near region of the release. Due to the non‐equilibrium nature of the near field regions accurate data measurement is not possible with intrusive techniques. Therefore, laser‐based optical techniques (like Particle Image Velocimetry (PIV), Particle Tracking Velocimetry and Sizing (PTVS), Phase Doppler Anemometry (PDA) etc.) present the only possibility to obtain information for particle diameter and velocity evolution in this harsh environment.     

Influence of Particle Morphology and Flow Conditions on the Dispersion Behavior of Fumed Silica in Silicone Polymers

The dispersion behavior of agglomerates of several grades of fumed silica in poly(dimethyl siloxane) liquids has been studied as a function of particle morphology and applied flow conditions. The effects of primary particle size and aggregate density and structure on cohesivity were probed through tensile and shear strength tests on particle compacts. These cohesivity tests indicated that the shear strength of particle compacts was two orders of magnitude higher than the tensile strength at the same overall packing density. Experiments carried out in both steady and time‐varying simple‐shear flows indicate that dispersion occurs through tensile failure. In the steady‐shear experiments,enhanced dispersion was obtained at higher levels of applied stress and, at comparable levels of applied stress, dispersion was found to proceed faster at higher shear rates. Experiments conducted in time‐varying flows further corroborated the results obtained in tensile cohesivity tests. Experiments in which the mean and maximum stresses in the time‐varying flows were matched to the stresses produced in steady shear flows highlight the influence of flow dynamics on dispersion behavior.     

Characterization of high-order harmonic radiation on femtosecond and attosecond time scales

We characterize the temporal structure of high-order harmonic radiation on both the femtosecond and attosecond time scales. The harmonic emission is characterized by mixed-color two-photon ionization with an infrared femtosecond laser using a Mach–Zehnder interferometer where both pump and probe arms travel completely separate paths. In a first experiment, we measure the duration and chirp of individual harmonics. In a second experiment, we resolve, for the first time with this type of setup, the attosecond beating of several harmonics generated under conditions similar to the first experiment. We suggest that the results of both measurements can be combined to determine the full attosecond time structure of the harmonic emission. PACS 32.80.Rm; 42.65.Ky     

Influence of preparation method on SrMoO4 impurity content and magnetotransport properties of double perovskite Sr2FeMoO6 polycrystals

The magnetic and electric properties of the Sr₂FeMoO₆ compound produced under different preparation conditions were studied. Depending on the preparation condition, a strong variation in the nonmagnetic SrMoO₄ impurity content was found, which in turn determined the metallic or semiconducting behavior of the resistivity of the Sr₂FeMoO₆ compound. There was also evidence that SrMoO₄ played a crucial role in modifying the low magnetic field intergrain tunneling magnetoresistance in Sr₂FeMoO₆. In addition, we have established a simple method to prepare the single phase Sr₂FeMoO₆ polycrystals.     

Transformations of cobalt trimethylacetate complexes with pyrazole upon oxidation by air in THF

Synthetic routes to oxidation of cobalt atoms in cobalt trimethylacetate complexes containing coordinated pyrazole molecules have been considered.