Nonlinear optical properties of regioregular main‐chain polyesters

We have prepared new polyesters containing quadratic, nonlinear optical (NLO) active chromophores covalently incorporated into the main chain. In these polymers, the sequence of the chromophore units along the main chain is rigorously head to tail. All the polyesters are processable, both in the melt and in solution. For one polyester, a full second‐order NLO characterization has been performed. An out‐of‐resonance d₃₃ coefficient of 21 pm/V at 1368 nm has been measured. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2719–2725, 2007     

Degradative chain transfer in vinyl acetate polymerizations using toluene as solvent

In this work, we propose that retardation in vinyl acetate polymerization rate in the presence of toluene is due to degradative chain transfer. The transfer constant to toluene (C_trs) determined using the Mayo method is equal to 3.8 × 10^?3, which is remarkably similar to the value calculated from the rate data, assuming degradative chain transfer (2.7 × 10^?3). Simulations, including chain‐length‐dependent termination, were carried out to compare our degradative chain transfer model with experimental results. The conversion–time profiles showed excellent agreement between experiment and simulation. Good agreement was found for the M_n data as a function of conversion. The experimental and simulation data strongly support the postulate that degradative chain transfer is the dominant kinetic mechanism. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3620–3625, 2007     

Influence of organic modifiers on morphology and crystallization of poly(ϵ‐caprolactone)/synthetic clay intercalated nanocomposites

ε‐caprolactone was polymerized in the presence of neat montmorillonite or organomontmorillonites to obtain a variety of poly(ε‐caprolactone) (PCL)‐based systems loaded with 10 wt % of the silicates. The materials were thoroughly investigated by different X‐ray scattering techniques to determine factors affecting structure of the systems. For one of the nanocomposites it was found that varying the temperature in the range corresponding to crystallization of PCL causes reversible changes in the interlayer distance of the organoclay. Extensive experimental and literature studies on this phenomenon provided clues indicating that this effect might be a result of two‐dimensional ordering of PCL chains inside the galleries of the silicate. Small angle X‐ray scattering and wide angle X‐ray scattering investigation of filaments oriented above melting point of PCL revealed that polymer lamellae were oriented perpendicularly to particles of unmodified silicate, while in PCL/organoclay systems they were found parallel to clay tactoids. Calorimetric and microscopic studies shown that clay particles are effective nucleating agents. In the nanocomposites, PCL crystallized 20‐fold faster than in the neat polymer. The crystallization rate in nanocomposites was also significantly higher than in microcomposite. Further research provided an insight how the presence of the filler affects crystalline fraction and spherulitic structure of the polymer matrix in the investigated systems. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2350–2367, 2007     

Variant superfield representations

We discuss some variant superfield representations which can arise by the replacement of some of the usual fields in a multiplet with p-form gauge fields.     

Prognostication of aging of polymeric composite materials

Experimental data demonstrate that a study of accelerated aging can enable prognostication of the working capacity and storage life of polymeric formulations used in aircraft components on the basis of changes in thermogravimetric constants of these polymeric formulations.     

Cosmic γ-ray bursts: Observations and modeling

It is now commonly accepted that cosmic γ-ray bursts (GRBs) are of cosmological origin. This conclusion is based on the statistical analysis of GRBs and the measurements of line redshifts in GRB optical afterglows, i.e., in the so-called long GRBs. In this review, the models of radiation and models of GRB sources are considered. In most of these models, if not in all of them, the isotropic radiation cannot provide the energy release necessary for the appearance of a cosmological GRB. No correlation is noted between the redshift, the GRB-spectrum shape, and the total detected energy. The comparison between data obtained in the Soviet experiment KONUS and the American experiment BATSE shows that they substantially differ in statistical properties and the detection of hard x-ray lines. The investigation of hard gamma (0.1–10 GeV) afterglows, the measurement of prompt optical spectra during the GRB detection, and the further investigation of hard x-ray lines is of obvious importance for gaining insight into the GRB origin. Observations of two bright optical GRB afterglows point to the fact that an initially bright optical flare is directly related to the GRB itself, and the subsequent weak and much more continuous optical radiation is of a different nature. The results of observations of optical GRB afterglows are discussed. They point to the fact that the GRBs originate in distant galaxies with a high matter density, where intense star formation takes place. The interaction of the cosmological GRB radiation with a dense surrounding molecular cloud results in the appearance of long-duration (up to 10 years) weak optical afterglows associated with the heating and reradiation of gas. Results of 2D numerical simulation of the heating and reradiation of gas in various variants of the relative disposition of GRB and molecular clouds are presented. In conclusion, the possible relation between the so-called short GRBs and recurrent sources of soft γ rays in our Galaxy, the so-called “soft gamma repeaters,” is discussed.     

Influence of the counterion size on swelling and collapse of polyelectrolyte gel

A theory that predicts the effect of the counterion size on the swelling and collapse of a weakly charged polyelectrolyte gel was developed. In addition to excluded-volume interactions between monomer units of the gel, the theory involves the counterion-monomer unit and counterion-counterion interactions in terms of the virial approximation. The character of interactions between different units in the system varies from repulsion to attraction depending on the type of solvent, counterion, and dielectric permittivity of the solvent. For solvents with a low permittivity, the effect of condensation of counterions resulting in the formation of ion pairs is taken into account.