Statistical thermodynamics evaluation of polymer–polymer miscibility

The Simha and Somcynsky (S–S) statistical thermodynamics theory was used to compute the solubility parameters as a function of temperature and pressure [δ = δ(T, P)], for a series of polymer melts. The characteristic scaling parameters required for this task, P*, T*, and V*, were extracted from the pressure–temperature–volume (PVT) data. To determine the potential polymer–polymer miscibility, the dependence of δ versus T (at ambient pressure) was computed for 17 polymers. Close proximity of the δ versus T curves for four miscible polymer pairs: PPE/PS, PS/PVME, and PC/PMMA signaled the usefulness of this approach. It is noteworthy, that the tabulated solubility parameters (derived from the solution data under ambient conditions) propounded the immiscibility of the PVC/PVAc pair. The computed values of δ also suggested miscibility for polymer pairs of unknown miscibility, namely PPE/PVC, PPE/PVAc, and PET/PSF. In recognizing the limitations of the solubility parameter approach (the omission of several thermodynamic contributions), these preliminary results are auspicious because they indicate a new route for estimating the miscibility of any polymeric material at a given temperature and pressure. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2909–2915, 2004     

The effect of crystallinity on chain mobility and free volume in the amorphous regions of a miscible polycarbonate/polyester blend

Homopolymers and blends of polycarbonate/ThermX have been investigated by differential scanning calorimetry, dynamic mechanical analysis, density measurements, and positron annihilation lifetime spectroscopy. The study focuses on the chain mobility and free volume in the amorphous miscible regions of the blends and how this mobility and free volume are affected by increasing crystallinity. It is proposed that judicious annealing, which results in increasing crystallinity (while avoiding ageing or transesterification), induces a constraint on the amorphous region leading to an increase in T_g and coalescence of free volume sites. © 1994 John Wiley & Sons, Inc.     

A hybrid finite-element–volume-of-fluid method for simulating free surface flows and interfaces

A numerical technique is developed for the simulation of free surface flows and interfaces. This technique combines the strength on the finite element method (FEM) in calculating the field variables for a deforming boundary and the versatility of the volume-of-fluid (VOF) technique in advection of the fluid interfaces. The advantage of the VOF technique is that it allows the simulation of interfaces with large deformations, including surface merging and breaking. However, its disadantage is that is solving the flow equations, it cannot resolve interfaces smaller than the cell size, since information on the subgrid scale is lost. Therefore the accuracy of the interface reconstruction and the treatment of the boundary conditions (i.e. viscous stresses and surface tension forces) become grid-size-dependent. On the other hand, the FEM with deforming interface mesh allows accurate implementation of the boundary conditions, but it cannot handle large surface deformations occurring in breaking and merging of liquid regions. Combining the two methods into a hybrid FEM-VOF method eliminates the major shortcomings of both. The outcome is a technique which can handle large surface deformations with accurate treatment of the boundary conditions. For illustration, two computational examples are presented, namely the instability and break-up of a capillary jet and the coalescence collision of two liquid drops.     

THE PARAMETER KERNELS FOR THE LINEAR INVERSION OF THE FREE OSCILLATION OF THE EARTH (Ⅰ)

In the linear inversion of the radial variation of the parameters of the Earth by usingthe observed frequencies of various normal modes of free oscillation of the earth, it is neces-sary to know the values of the kernels of the parameters ρ, μ and λ. This paper describesthe methods of the derivation of the formulas of these kernels. This is the first part of thepaper in which only the toroidal oscillations are considered. They are much simpler thanthose of the spheroidal ones, that we will consider in the second part of the paper. The data of the two types of oscillations are equally important in the solution of theinversion problem, and should be employed simultaneously, and we know that the toroidaloscillations are much simpler than the spheroidal ones, it seems wise to divide the whole programof the inversion problem into steps: first, by employing the toroidal data to correct the twoparameters ρ and μ in the mantle, then by using the spheroidal data to correct the remain-ing parameters, i.e. th     

Modeling and simulation of free radical polymerization of styrene under semibatch reactor conditions

The first part of this approach is concerned with the elaboration of a radical polymerization model of styrenne, based on a kinetic diagram that includes chemical and thermal initiation, propagation, termination by recombination and chain transfer to the monomer. Furthermore, volume contraction during polymerization is considered, as well as the gel and glass effects. The mathematical formalism that describes the model in terms of moments is explored in detail. The model was then used to predict the changes in monomer conversion and molecular weight after intermediate addition of initiator and monomer. The results of this operation are dependent on the conditions of the reaction mass, quantity, and moment of substance addition. Therefore, the simulations were performed at different times with respect to the gel effect; before, during and after this phenomenon, and also with respect to different temperatures and initiators. Increasing the initiator concentration before the gel effect leads to an earlier appearance of the phenomenon and to a decrease in molecular weight. The ratio reveals a polydispersity index smaller for the intermediate addition of initiator. No significant changes take place during or after the gel effect. If along with the initiator, unreacted monomver (used to dissolve the initiator) enters the reactor, a small dip in conversion is observed. The general conclusion of this paper reveals the intermediate addition of initiator as a method to control polymer properties and to prevent the “dead-end” polymerization of styrene.     

Lipids from Five Cotton Varieties

Seed characteristics and the lipid and fatty-acid compositions were determined for the new cotton varieties ASh-25, Omad, 9771-I, Termez-43, and Bukhara-6.     

Degradation in gain for a free electron laser amplifier due to electron momentum spread

A finite spread in axial momentum for the electron beam in a free electron laser amplifier is shown to decrease the small-signal gain. For millimeter and sub-millimeter wave amplifiers, where exponential growth dominates the gain, it is shown that the gain is approximately 3 db below that for a cold beam if the relative momentum spread (u/u)_1/2 = (G_o/248)^1/2 (_o/L), where G_o1 is the gain in db for the cold-beam case, _o is the magnetic wiggler period, and L is the amplifier length. Exact numerical examples are given for representative FEL amplifiers at 35 and 550 GHz.This research was sponsored by the U.S. Office of Naval Research, and by the U.S.-Israel Binational Science Foundation.     

Characterization and Bioavailability of Vitamin C Nanoliposomes Prepared by Film Evaporation-Dynamic High Pressure Microfluidization

Vitamin C nanoliposomes were prepared by combining a conventional method (film evaporation) with dynamic high pressure microfluidization. Their physicochemical characterizations (antioxidant activity, particle size, entrapment efficiency, morphology, in vitro drug release, and storage stability) and skin permeation behavior were investigated. The results showed that vitamin C nanoliposomes, having equivalent DPPH (2, 2-diphenyl-1-picrylhydrazyl) free radical scavenging capacity of pure vitamin C solution without loss of their biological activity, exhibited better storage stability at 37°C for 24 hours and at 4°C for 60 days, a more excellent sustained drug release as well as higher skin penetration rate than vitamin C liposomes.     

On the stationary measures of anharmonic systems in the presence of a small thermal noise

We consider certain small stochastic perturbations of ad-dimensional infinite system of coupled anharmonic oscillators. The evolution law is reversible in the Yaglom sense, thus Gibbs states with the given interaction and temperature are stationary measures. If d<3 then some stability properties of the interaction imply the converse statement; if d>2 then the same is proven for translation invariant measures only. The methods and results of Ref. 4, 6–8 are extended to second-order systems of stochastic differential equations.