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     

Quantification of trace elements in human serum fractions by liquid chromatography and inductively coupled plasma mass spectrometry

On‐line coupling of LC and ICP‐MS has been used for fractionation and detection of species of Cu, Fe, I, Se and Zn in human serum. It has been shown that anion exchange chromatography provided better separation capability (both intra‐ and inter‐element) than size‐exclusion chromatography. The mobile phases for ion exchange chromatography consisted of Tris–HNO₃ buffer and ammonium salt (nitrate, acetate or formate). Formate was found to be the best mobile phase counter ion, enabling good chromatographic separation, and is acceptable for mass spectrometry too. The quantitative evaluation of element concentrations adhering to individual fractions was performed by the peak area normalization method. The repeatability of results ranged from 3 to 15% (depending on the element concentration level) and represented the main part of the result uncertainty. The accuracy of Cu and Zn fraction determinations was confirmed by comparison with the isotope dilution technique. Copyright © 2006 John Wiley & Sons, Ltd.     

Structure of norbornene-fused 3,1-oxazine double cycloadducts

Pentacyclic isoxazolines were obtained by the cycloaddition of benzonitrile oxide to norbornene-azetidinone-fused 3,1-oxazines. The constitutions of two of the isomers obtained, and the configurations and conformations of all products, were determined by means of ¹H and ¹³C NMR spectroscopy and DNOE experiments.     

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.     

Studies on calcium‐containing poly(urethane ether)s

The calcium salt of mono(hydroxyethoxyethyl)phthalate [Ca(HEEP)₂] was synthesized by the reaction of diethylene glycol, phthalic anhydride, and calcium acetate. Calcium‐containing poly(urethane ether)s (PUEs) were synthesized by the reaction of hexamethylene diisocyanate (HMDI) or tolylene 2,4‐diisocyanate (TDI) with a mixture of Ca(HEEP)₂ and poly(ethylene glycol) (PEG₃₀₀ or PEG₄₀₀) with di‐n‐butyltin dilaurate as a catalyst. A series of calcium‐containing PUEs of different compositions were synthesized with Ca(HEEP)₂/PEG₃₀₀ (or PEG₄₀₀)/diisocyanate (HMDI or TDI) molar ratios of 2:2:4, 3:1:4, and 1:3:4 so that the coating properties of the PUEs could be studied. Blank PUEs without calcium‐containing ionic diols were also prepared by the reaction of PEG₃₀₀ or PEG₄₀₀ with HMDI or TDI. The PUEs were well characterized by Fourier transform infrared, ¹H and ¹³C NMR, solid‐state cross‐polarity/magic‐angle‐spinning ¹³C NMR, viscosity, solubility, and X‐ray diffraction studies. The thermal properties of the polymers were also studied with thermogravimetric analysis and differential scanning calorimetry. The PUEs were applied as top coats on acrylic‐coated leather, and their physicomechanical properties were also studied. The coating properties of PUEs, such as the tensile strength, elongation at break, tear strength, water vapor permeability, flexing endurance, cold crack resistance, abrasion resistance, color fastness, and adhesive strength, were better than the standard values. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2865–2878, 2003