Sterically stabilized emulsion polymerization of styrene: Pseudo‐semicontinuous approach

The sterically stabilized emulsion polymerization of styrene initiated by a water‐soluble initiator at different temperatures has been investigated. The rate of polymerization (R_p) versus conversion curve shows the two non‐stationary‐rate intervals typical for the polymerization proceeding under non‐stationary‐state conditions. The shape of the R_p versus conversion curve results from two opposite effects—the increased number of particles and the decreased monomer concentration at reaction loci as the polymerization advances. At elevated temperatures the monomer emulsion equilibrates to a two‐phase or three‐phase system. The upper phase is transparent (monomer), and the lower one is blue colored, typical for microemulsion. After stirring such a multiphase system and initiation of polymerization, the initial coarse polymer emulsion was formed. The average size of monomer/polymer particles strongly decreased up to about 40% conversion and then leveled off. The initial large particles are assumed to be highly monomer‐swollen particles formed by the heteroagglomeration of unstable polymer particles and monomer droplets. The size of the “highly monomer” swollen particles continuously decreases with conversion, and they merge with the growing particles at about 40–50% conversion. The monomer droplets and/or large highly monomer‐swollen polymer particles also serve as a reservoir of monomer and emulsifier. The continuous release of nonionic (hydrophobic) emulsifier from the monomer phase increases the colloidal stability of primary particles and the number of polymer particles, that is, the particle nucleation is shifted to the higher conversion region. Variations of the square and cube of the mean droplet radius with aging time indicate that neither the coalescence nor the Ostwald ripening is the main driving force for the droplet instability. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 804–820, 2003     

Microemulsion polymerization of styrene in the presence of a cationic emulsifier

The principal subject discussed in the current paper is the radical polymerization of styrene in the three- and four component microemulsions stabilized by a cationic emulsifier. Polymerization in the o/w microemulsion is a new polymerization technique which allows to prepare the polymer latexes with the very high particle interface area and narrow particle size distribution. Polymers formed are very large with a very broad molecular weight distribution. In emulsion and microemulsion polymerizations, the reaction takes place in a large number of isolated loci dispersed in the continuous aqueous phase. However, in spite of the similarities between emulsion and microemulsion polymerization, there are large differences caused by the much larger amount of emulsifier in the latter process. In the emulsion polymerization there are three rate intervals. In the microemulsion polymerization only two reaction rate intervals are commonly detected: first, the polymerization rate increases rapidly with the reaction time and then decreases steadily. Essential features of microemulsion polymerization are as follows: (1) polymerization proceeds under non-stationary state conditions; (2) size and particle concentration increases throughout the course of polymerization; (3) chain-transfer to monomer/exit of transferred monomeric radical/radical re-entry events are operative; and (4) molecular weight is independent of conversion and distribution of resulting polymer is very broad. The number of microdroplets or monomer-starved micelles at higher conversion is high and they persist throughout the reaction. The high emulsifier/water ratio ensures that the emulsifier is undissociated and can penetrate into the microdroplets. The presence of a large amount of emulsifier strongly influences the reaction kinetics and the particle nucleation. The mixed mode particle nucleation is assumed to govern the polymerization process. At low emulsifier concentration the micellar nucleation is dominant while at a high emulsifier concentration the interaction-like homogeneous nucleation is operative. Furthermore, the paper is focused on the initiation and nucleation mechanisms, location of initiation locus, and growth and deactivation of latex particles. Furthermore, the relationship between kinetic and molecular weight parameters of the microemulsion polymerization process and colloidal (water/particle interface) parameters is discussed. In particular, we follow the effect of initiator and emulsifier type and concentration on the polymerization process. Besides, the effects of monomer concentration and additives are also evaluated.     

On acrylonitrile polymerization in the presence of zinc salts

Acrylonitrile polymerization photoinitiated at 365 nm by pyrene and/or azobisisobutyronitrile in the presence of zinc salts in N,N-dimethylformamide solution has been studied by the rotating sector method. It was found that the ratio of the rate constants for propagation and termination (k_p/k_t) increases on addition of zinc salts (chloride, nitrate, acetate). This increase was more pronounced for the azobisisobutyronitrile photoinitiated polymerization of acrylonitrile then for its pyrene photoinitiated polymerization. The results confirm the previously expressed view concerning the dual role of zinc chloride in initiation as well as in propagation steps of acrylonitrile polymerization photoinitiated by aromatic hydrocarbons.

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Black holes in massive gravity: quasi-normal modes of scalar perturbations

We have studied quasinormal modes of scalar perturbations of a black hole in massive gravity. The parameters of the theory, such as the mass of the black hole, the scalar charge of the black hole and the spherical harmonic index is varied to see how the corresponding quasinormal frequencies change. We have also studied the massive scalar field perturbations. Most of the work is done using WKB approach while sections are devoted to compute quasinormal modes via the unstable null geodesics approach and the Pöschl–Teller approximation. Comparisons are done with the Schwarzschild black hole.     

Learning a novel phonological contrast depends on interactions between individual differences and training paradigm design

Studies evaluating phonological contrast learning typically investigate either the predictiveness of specific pretraining aptitude measures or the efficacy of different instructional paradigms. However, little research considers how these factors interact--whether different students learn better from different types of instruction--and what the psychological basis for any interaction might be. The present study demonstrates that successfully learning a foreign-language phonological contrast for pitch depends on an interaction between individual differences in perceptual abilities and the design of the training paradigm. Training from stimuli with high acoustic-phonetic variability is generally thought to improve learning; however, we found high-variability training enhanced learning only for individuals with strong perceptual abilities. Learners with weaker perceptual abilities were actually impaired by high-variability training relative to a low-variability condition. A second experiment assessing variations on the high-variability training design determined that the property of this learning environment most detrimental to perceptually weak learners is the amount of trial-by-trial variability. Learners' perceptual limitations can thus override the benefits of high-variability training where trial-by-trial variability in other irrelevant acoustic-phonetic features obfuscates access to the target feature. These results demonstrate the importance of considering individual differences in pretraining aptitudes when evaluating the efficacy of any speech training paradigm.     

Moduli of twisted spin curves

In this note we give a new, natural construction of a compactification of the stack of smooth -spin curves, which we call the stack of stable twisted -spin curves. This stack is identified with a special case of a stack of twisted stable maps of Abramovich and Vistoli. Realizations in terms of admissible -spaces and -line bundles are given as well. The infinitesimal structure of this stack is described in a relatively straightforward manner, similar to that of usual stable curves.

We construct representable morphisms from the stacks of stable twisted -spin curves to the stacks of stable -spin curves and show that they are isomorphisms. Many delicate features of -spin curves, including torsion free sheaves with power maps, arise as simple by-products of twisted spin curves. Various constructions, such as the -operator of Seeley and Singer and Witten's cohomology class go through without complications in the setting of twisted spin curves.