Competitive influence of atactic polystyrene and supercritical carbon dioxide on the conformation of syndiotactic polystyrene

The crystallization behavior of miscible syndiotactic polystyrene (sPS) and atactic polystyrene (aPS) blends with different sPS/aPS weight ratios was investigated in supercritical CO₂ by using Fourier‐transform infrared spectroscopy, differential scanning calorimetry, and wide‐angle X‐ray diffraction. Supercritical CO₂ and aPS exhibited different effects on the conformational change of sPS and competed with each other. Increasing the content of amorphous aPS in the blends made its effect on the conformational change of sPS gradually surpass that of supercritical CO₂. Supercritical CO₂ favored the formation of the helical conformation of sPS in lower temperature range and the all trans planar conformation in higher temperature range, instead of forming the latter one only in higher temperature range in ambient atmosphere. However, increasing aPS content in the blends pushed the range for forming the helical conformation to lower temperature and made the all trans planar conformation dominant in aPS/sPS 25/75 blend after treating in supercritical CO₂ above 60 °C. The all trans planar zigzag conformation was more favorable than the helical conformation after mixing aPS in sPS in supercritical CO₂. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1755–1764, 2007     

Synthesis of graft copolymers with “V‐shaped” and “Y‐shaped” side chains via controlled radical and anionic polymerizations

A combination of nitroxide‐mediated radical polymerization and living anionic polymerization was used to synthesize a series of well‐defined graft (co)polymers with “V‐shaped” and “Y‐shaped” branches. The polymer main chain is a copolymer of styrene and p‐chloromethylstyrene (PS‐co‐PCMS) prepared via nitroxide‐mediated radical polymerization. The V‐shaped branches were prepared through coupling reaction of polystyrene macromonomer, carrying 1,1‐diphenylethylene terminus, with polystyryllithium or polyisoprenyllithium. The Y‐shaped branches were prepared throughfurther polymerization initiated by the V‐shaped anions. The obtained branches, carrying a living anion at the middle (V‐shaped) or at the end of the third segment (Y‐shaped), were coupled in situ with pendent benzyl chloride of PS‐co‐PCMS to form the target graft (co)polymers. The purified graft (co)polymers were analyzed by size exclusion chromatography equipped with a multiangle light scattering detector and a viscometer. The result shows that the viscosities and radii of gyration of the branched polymers are remarkably smaller than those of linear polystyrene. In addition, V‐shaped product adopts a more compact conformation in dilute solution than the Y‐shaped analogy. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4013–4025, 2007     

A co‐ordinate system independent streamwise upwind method for fluid flow computation

A new co‐ordinate invariant streamwise upwind formulation for convection dominated flows is developed. The eddy diffusivity/viscosity is added directly to the equations in order to remove the oscillations in the solution. The equations then can be solved by any high‐order scheme and the solution retains the accuracy of the high‐order scheme. The accuracy and reduced lateral thickness growth rate are demonstrated with several numerical examples, including pure convective flows and lid‐driven cavity flow. The lateral spreading due to the numerical diffusion is controlled by the anisotropic tensor. Copyright © 2004 John Wiley & Sons, Ltd.     

Application of ultrafine-dispersed diamonds in electroplating

The results obtained upon the electrochemical deposition of composite coatings containing ultrafine-dispersed diamonds produced by detonation synthesis are generalized. The main advantages of such coatings over the well-known composite electrochemical coatings are revealed.     

Modeling of the structure and electronic structure of condensed phases of small fullerenes C<Subscript>28</Subscript> and Zn@C<Subscript>28</Subscript>

A comparative analysis of the stability factors and electronic structure of two possible crystalline forms of small fullerene C₂₈ and endohedral fullerene Zn@C₂₈ with diamond and lonsdaleite structures is performed using a cluster model. Atoms of elements that, when placed inside C₂₈ cages, have no significant effect on the stability of free small-fullerene molecules are shown to be able to dramatically change the electronic properties and reactivity of the C₂₈ skeleton and to be favorable for forming small-fullerene crystalline modifications, which are covalent crystals. In contrast, if the presence of foreign atoms inside C₂₈ cages stabilizes the isolated nanoparticles, then molecular crystals (such as C₆₀ fullerites) are formed due to weak van der Waals forces.     

Crystallographic report: Crystal structure of tetra(4‐methyl‐5‐imidazole‐carboxyaldehyde)zinc(II) diperchlorate

The central zinc(II) atom in the title complex is tetrahedrally coordinated by four nitrogen atoms derived from 4‐methyl‐5‐imidazolecarboxyaldehyde ligands with Zn? N in the range 2.007(3) to 2.026(4) Å. Copyright © 2003 John Wiley & Sons, Ltd.     

On a Countable-Point Nonlinear Boundary-Value Problem on a Semiaxis for Ordinary Differential Equations in the Space of Bounded Numerical Sequences

We use the idea of the Samoilenko numerical-analytic method for the investigation of a nonlinear boundary-value problem with an unbounded countable set of boundary moments on the positive semiaxis in the case where the differential equation and boundary conditions are defined in the Banach space of bounded numerical sequences.     

Synthesis of side‐chain liquid‐crystalline homopolymers and triblock copolymers with p‐methoxyazobenzene moieties and poly(ethylene glycol) as coil segments by atom transfer radical polymerization and their thermotropic phase behavior

A series of side‐chain liquid‐crystalline (LC) homopolymers of poly[6‐(4‐methoxy‐4′‐oxy‐azobenzene) hexyl methacrylate] with different degrees of polymerization were synthesized by atom transfer radical polymerization (ATRP), which were prepared with a wide range of number‐average molecular weights from 5.1 × 10³ to 20.6 × 10³ with narrow polydispersities of around 1.17. Thermal investigation showed that the homopolymers exhibit two mesophases, a smectic phase, and a nematic phase, and the phase‐transition temperatures of the homopolymers increase clearly with increasing molecular weights. A series of novel LC coil triblock copolymers with narrow polydispersities was synthesized by ATRP, and their thermotropic phase behavior was investigated with differential scanning calorimetry and polarized optical microscopy. The LC coil triblocks were designed to have an LC conformation of poly[6‐(4‐methoxy‐4′‐oxy‐azobenzene) hexyl methacrylate] with a wide range of molecular weights from 3.5 × 10³ to 1.7 × 10⁴ and the coil conformation of poly(ethylene glycol) (PEG) (number‐average molecular weight: 6000 or 12,000) segment. Their characterization was investigated with ¹H NMR, Fourier transform infrared spectra, and gel permeation chromatography. Triblock copolymers exhibited a crystalline phase, a smectic phase, and a nematic phase. The phase‐transition temperatures from the smectic to nematic phase and from the nematic to isotropic phase increased, and the crystallization of PEG depressed with increasing molecular weight of the LC block. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2854–2864, 2003     

Search for the emission of π<Superscript>0</Superscript> mesons from the neutron-induced fission of <Superscript>235</Superscript>U nuclei

A nuclear-reactor experiment on the search for the emission of neutral pions from the neutron-induced fission of ²³⁵U nuclei has been carried out. To this end, an experimental setup for searching for the emission of π⁰ mesons with high sensitivity to this process has been designed and produced. This setup consisted of two Cherenkov total-absorption spectrometers for the detection and measurements of the energy of two gamma-ray photons from π ⁰-meson decay. The spectrometers were placed at the exits of two coaxial horizontal experimental channels. To protect the detectors from low-energy β and γ rays and neutron fluxes, 3.5-m-long water filters were situated in the channels. To reject the cosmic background, large-area scintillation counters operating in the anticoincidence mode were placed over each spectrometer. The energy and time resolution of the spectrometers, as well as the efficiency of detecting charged particles by scintillation counters, were tested on the secondary electron beam of the Tomsk electron synchrotron Sirius. Runs of measurements of the effect on the operating reactor (duration of 805 h) were alternated with runs of measurements of background on the stopped reactor (duration of 403 h). Statistical processing of the experimental results yields an upper limit of ≤5.3×10 ^?12 with a 90% confidence level for the probability of the emission of neutral pions from the neutron-induced fission of ²³⁵U nuclei. This result and results of other works carried out with sources of spontaneously fissioning ²⁵²Cf nuclei show that the probabilities of the emission of π⁰ mesons from spontaneous fission and fission induced by fission-spectrum neutrons are equal to each other.