Glass transition of miscible binary polymer-polymer thin films

The average glass transition temperatures, Tg, of thin homopolymer films exhibit a thickness dependence, Tg(h), associated with a confinement effect and with polymer-segment-interface interactions. The Tg's of completely miscible thin film blends of tetramethyl bisphenol-A polycarbonate (TMPC) and deuterated polystyrene (dPS), supported by SiO(x)/Si, decrease with decreasing h for PS weight fractions phi >0.1. This dependence is similar to that of PS and opposite to that of TMPC thin films. Based on an assessment of Tg(h, phi), we suggest that the Tg(h, phi) of miscible blends should be rationalized, additionally, in terms of the notion of a self-concentration and associated heterogeneous component dynamics.     

Thermodynamic and kinetic study of the single extraction of mercury from soil using sodium-thiosulfate

The use of sodium-thiosulfate (Na-thiosulfate) as a reagent for the extraction of mercury (Hg) from soil was investigated. High organic matter content in soil plays a major role in retaining metals. It has previously been reported that using the cold vapour atomic absorption method, powerful reagents such as EDTA, DTPA and cysteine could not release Hg from soil samples. The optimal conditions for using Na-thiosulfate to extract soil-Hg are presented here. Our results show that 50 ± 5% of total Hg was extracted from soil samples using 0.01 mol L⁻¹ of the reagent without pH adjustment. Increasing the reagent concentration above this level showed no significant change in Hg extraction. From this extraction three fractions of Hg were obtained, the labile, slowly labile and un-extractable. We further applied the use of a kinetic extraction approach that has never been applied for Hg. We observed a correlation between the first two fractions and the quantity of organic matter content in soils. The labile fraction could be released by using any concentration of the reagent. However, the slowly labile fraction was dependent on time and increased concentrations of Na-thiosulfate. Furthermore, our results suggest that the labile and slowly labile fractions involve two different sites of reduced sulphur groups contained in soil organic matter and Hg levels present in the soil samples did not appear high enough to saturate all these high affinity sulphur sites. The capacity of Na-thiosulfate to reduce (Hg(II)) to (Hg(0)), was determined to be negligible. Our results further suggest the implication of iron (Fe(II)) for reducing Hg(II) to Hg(0). Here we have demonstrated that Na-thiosulfate is an effective reagent in the extraction of Hg from soil, with the particular characteristic of its ability to remove strongly bound Hg from sulphur groups contained in soil organic matter.     

The discretized flow on domains of attraction: a structural stability result

It is well known that, for stepsize sufficiently small, compactattractors of ordinary differential equations persist underdiscretization. The present paper describes the structure ofthe discrete-time dynamical system obtained via discretizationon A(M_h)\M_h where M_h is the approximate attractor and A(M_h)is its domain of attraction. The existence of a smooth embeddinginto a continuous-time parallelizable flow is proved. The constructioncan be used to define sections for discretizations and can beinterpreted as a justification of the method of modified equations.     

Comparison of Dry Test Sieving on Woven Wire Cloths versus electroformed sheets

Dry test sieving results given by woven wire cloths with a square mesh and by round electroformed apertures were compared using sands of various origin. The difference has been found to be constant and independent of substance and quantile. The quantile obtained on a square mesh was converted into the corresponding quantile on an electroformed sheet of the same nominal aperture by multiplication by a constant factor of 1.21 ± 0.04.     

Problems de stereochimie dynamique en serie du titanocene : II. Stereochimie dynamique de reactions déchange de ligands σ-lies

Two ligand exchange reactions at the titanium atom in quasi-tetrahedral titanocene complexes have been studied. The first is substitution of a Cl ligand by an aryloxy group starting from substrates η⁵-Cp-η⁵-Cp′Ti(Cl)OPh which have an planar chirality on the Cp′ ring. The second is the substitution of one of the aryloxy groups of the complexes η⁵-Cp-η⁵-Cp′Ti(OPh′)OPh by the action of HCl. In this case, the reaction is generally selective and has a high degree of stereo-specificity with retention at the titanium atom. This retention has been established by crystallographic analysis of two suitable substrates: diastereoisomer F. 171°C of η⁵-C₅H₅[η⁵-(1-Me-3-CHMe₂C₅H₅)](2-ClC₆H₄O)(2,6-Me₂C₆H₃O)Ti and diastereoisomer F. 134°C of η⁵-C₅H₅[η⁵-(1-Me-3-CHMe₂C₅H₃)](2-ClC₆H₄O)TiCl.     

Diastéréotopies dans la série du benchrotrène

¹H and ¹³C spectra of mono-and disubstituted (benzene)-tricarbonylchromium complexes have been analysed. The influence of the substituents is discussed and special attention is paid to the diastereotopy resulting from different types of chirality. The racemic pseudosymmetric isomer and the two meso pseudoasymmetric isomers of the glycols (OC)₃CrC₆H₄(CHOHCH₃)₂ are compared. The stereochemical requirements are also examined.     

Dynamics of arrays of cylinders with internal and external axial flow

Various aspects of the dynamics and stability of clusters of tubular cylinders containing internally flowing fluid and surrounded by a bounded external axial flow are examined. The general character of free motions is established by obtaining the eigenfrequencies of the system and studying their evolution with increasing flow, internal or external. Stability diagrams have been obtained for the critical flow velocities, beyond which the system would lose stability by buckling (divergence), under the combined effect of internal and external flow. Free vibration, following an initial disturbance of one of the cylinders, is studied, in order further to examine the effect of hydrodynamic coupling. It is found that beating phenomena may arise, implying energy transfer between cylinders and the possibility of transient amplitudes much larger than the initial disturbances. Also, the vibration of the system (in still fluid) when one cylinder is constrained to oscillate in a prescribed manner is examined, establishing that transmission of vibration from cylinder to cylinder can be very rapid; indeed, such constrained motion of one cylinder at certain frequencies may induce large amplified motions of others.     

Dewetting dynamics in miscible polymer-polymer thin film mixtures

Thin polystyrene films supported by oxidized silicon (SiOx/Si) substrates may be unstable or metastable, depending on the film thickness, h, and can ultimately dewet the substrate when heated above their glass transition. In the metastable regime, holes nucleate throughout the film and subsequently grow due to capillary driving forces. Recent studies have shown that the addition of a second component, such as a copolymer or miscible polymer, can suppress the dewetting process and stabilize the film. We examined the hole growth dynamics and the hole morphology in thin film mixtures composed of polystyrene and tetramethyl bisphenol-A polycarbonate (TMPC) supported by SiOx/Si substrates. The hole growth velocity decreased with increasing TMPC content beyond that expected from changes in the bulk viscosity. The authors show that the suppression of the dewetting velocity is primarily due to reductions in the capillary driving force for dewetting and to increased friction at the substrate-polymer interface. The viscosity, as determined from the hole growth dynamics, decreases with decreasing film thickness, and is connected to a depression of the glass transition of the film.