On the evaluation of the nonisothermal kinetic parameters of (GeS2)0.3(Sb2S3)0.7 crystallization using the IKP method

The isoconversional method suggested by Friedman and the invariant kinetic parameters method (IKP) were used in order to examine the kinetics of the nonisothermal crystallization of (GeS₂)_0.3(Sb₂S₃)_0.7. The objective of the paper is to show the usefulness of the IKP method both for determining the activation parameters as well as the model of the investigated process. It was shown that the kinetic triplet [(E, A, f(α), where E is the activation energy, A is the preexponential factor, and f(α) is the differential function of conversion], which results through the application of the IKP method, depends on the set of kinetic models considered. For different sets of kinetic models, proportional values of f(α) are obtained. A criterion for the selection of this set, the use of which lead to the true kinetic triplet corresponding to the analyzed process (E = 163.2 kJ mol^?1; A = 2.47 × 10¹² min^?1 and the Avrami‐Erofeev model, A_m, for m = 2.5–2.6 was suggested. © 2004 Wiley Periodicals, Inc. Int J Chem Kinet 36: 309–315, 2004     

Complex morphology of melt-spun nylon-6 fibres investigated by 1H double-quantum-filtered NMR spin-diffusion experiments.

The complex morphology of high-speed melt-spun nylon-6 fibres hydrated with D2O was investigated using 1H double-quantum-filtered spin-diffusion NMR experiments. The magnetisation exchange from selected crystalline domains along the fibrils and interfibrils was simulated with the help of a three-dimensional solution of a spin-diffusion equation approximated by a product of one-dimensional analytical NMR signals, which correspond to a lamellar morphology. This allows to measure the sizes of crystalline and less-mobile amorphous domains along the fibrils, as well as the diameter of the fibrils and interfibril distances. A series of nylon-6 fibres with extreme values of winding speed and draw ratio was investigated. The changes detected in the domain size along the fibrils and interfibrils show the same trend in the data obtained from wide-angle X-ray diffraction and small-angle X-ray scattering.     

Reverse micellar synthesis and properties of nanocrystalline GMR materials (LaMnO3, La0.67Sr0.33MnO3 and La0.67Ca0.33MnO3): Ramifications of size considerations

Nanoparticles of complex manganites (viz. LaMnO₃, La_0.67Sr_0.33MnO₃ and La_0.67Ca{0.33}MnO₃) have been synthesized using the reverse micellar route. These manganites are prepared at 800‡C and the monophasic nature of all the oxides has been established by powder X-ray diffraction studies. TEM studies show an average grain size of 68, 80 and 50 nm for LaMnO₃, La_0.67Sr_0.33MnO₃ and La_0.67Ca{0.33}MnO₃respectively. Ferromagnetic ordering is observed at around 250 K for LaMnO₃, 350 K for La_0.67Sr_0.33MnO₃ and 200 K for La_0.67Ca{0.33}MnO₃. These Curie temperatures correspond well with those reported for bulk materials with similar composition.     

Technology for producing adsorbents from petroleum residues

Advantage of use residue from thermal cracking and products of its condensation as components of the mixture for manufacturing mechanically rigid (93%) granulated and ground carbon sorbents with extended volume of micropores (up to 0.27 cm³/cm³), showing enhanced sorption activity (E is up to 25.6 kJ mol^?1) and high ability of separation various gas mixtures is demonstrated. As a carrier for medicine preparations these adsorbents show higher performance as compared with industrial samples. Solutions of the cracking residue can be used for impregnation of worked out zeolites for petroleum technology and for production of organomineral adsorbents with high adsorption capacity on extraction mercury from sewages.     

Evaluation of the capillary pressure in a liquid interlayer between the particles of a dispersed phase

The capillary pressure in a liquid interlayer between two spherical particles is calculated as a function of their sizes and the wetting properties of the liquid.     

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     

Thickness dependence of free‐standing thin films

Below a critical thickness, of about 60 nm, the glass transition temperature of polystyrene (PS) films decreases with film thickness, as demonstrated using free‐standing films. A geometrical model is developed here describing this phenomenon in the case of ideal (Gaussian) chains. This model, which can be considered as an application of the free volume model, assumes that the decrease of the glass transition temperature from thick to ultrathin films is due to the modification of the interpenetration between neighboring chains. The theoretical curve deduced from the model is in excellent agreement with the PS experimental results, without using any adjustable parameters. From these results, it can be concluded that new chain motions, usually buried in bulk samples, are expressed by the presence of the surface. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 10–17, 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.     

Transient free‐surface flow of a viscoelastic fluid in a narrow channel

The interplay between inertia and elasticity is examined for transient free‐surface flow inside a narrow channel. The lubrication theory is extended for the flow of viscoelastic fluids of the Oldroyd‐B type (consisting of a Newtonian solvent and a polymeric solute). While the general formulation accounts for non‐linearities stemming from inertia effects in the momentum conservation equation, and the upper‐convected terms in the constitutive equation, only the front movement contributes to non‐linear coupling for a flow inside a straight channel. In this case, it is possible to implement a spectral representation in the depthwise direction for the velocity and stress. The evolution of the flow field is obtained locally, but the front movement is captured only in the mean sense. The influence of inertia, elasticity and viscosity ratio is examined for pressure‐induced flow. The front appears to progress monotonically with time. However, the velocity and stress exhibit typically a strong overshoot upon inception, accompanied by a plug‐flow behaviour in the channel core. The flow intensity eventually diminishes with time, tending asymptotically to Poiseuille conditions. For highly elastic liquids the front movement becomes oscillatory, experiencing strong deceleration periodically. A multiple‐scale solution is obtained for fluids with no inertia and small elasticity. Comparison with the exact (numerical) solution indicates a wide range of validity for the analytical result. Copyright © 2004 John Wiley & Sons, Ltd.