Thermally stimulated current spectra in nitrogen implanted fluorinated ethylene propylene

Thermally stimulated current spectra of nitrogen implanted fluorinated ethylene propylene polymer foils have been studied. Two characteristic peaks have been obtained for samples implanted with nitrogen ions with energies ranging from 20 to 60 keV. The variations in the activation energies and relaxation times of charge carriers, as a function of implantation energy, have been attributed to the corresponding changes in the carrier distribution in the polymer. The carrier mobilities and mobility life-time products have also been estimated for the two characteristic peaks.     

Schiff base derivatives of titanium(IV) and zirconium(IV)

The reactions of a few bifunctional and tridentate Schiff bases with titanium-(IV) and zirconium(IV) isopropoxides in equimolar and bimolar ratios are described. The resulting compounds have been obtained in almost quantitative yields and are of the general formulae M(SB)_x(OPrⁱ)_4?2X (where M = Ti or Zr; SB- = anion of the Schiff base SBH₂ and x = 1 or 2). Their molecular weights have been determined ebullioscopically and IR spectra recorded.     

A redox-mediated molecular brake: dynamic NMR study of 2-[2-(methylthio)phenyl]isoindolin-1-one and S-oxidized counterparts

A redox-mediated molecular brake based on the sulfide-sulfoxide redox cycle is illustrated by modulation of the rotation rate of an N-Ar "shaft" by varying the oxidation state of sulfur in 2-[2-(sulfur-substituted)phenyl]isoindolin-1-ones. N-Ar rotational barriers in methylsulfinyl (2) and methylsulfonyl (3) derivatives (13.6 kcal mol(-1)) are approximately 5 kcal mol(-1) higher than sulfide 1. Rate reduction for N-Ar rotation is approximately 10(4) s(-1) (280 K) upon oxidation. Correlated N-pyramidalization/N-Ar rotation reduces the effectiveness of the brake by decreasing the energy barrier to N-Ar bond rotation.     

Simple rhodium-chlorophosphine pre-catalysts for the ortho-arylation of phenols

Simple chlorodiisopropylphosphine adducts of rhodium, either pre-formed or formed in situ, prove to be highly effective catalysts for the ortho-arylation of phenols.     

Modified interfacial statistical associating fluid theory: application to tethered polymer chains

Modified interfacial statistical associating fluid theory density functional theory is extended to tethered polymer chains in the absence or presence of free polymer chains. The structures of the "dry" and "wet" polymer brushes have been calculated and compared with simulation results available in the literature. The comparisons show that the theory accurately predicts the structure of the tethered polymer brush. The average brush heights calculated from the theory agree with well-established scaling theories for tethered polymers. However, these scaling theories cannot predict the detailed structure, accurately. The effects of the segment-segment interactions of the tethered polymer and the free polymer have been effectively captured by the theory.     

Nonlinear instability of an annular liquid sheet exposed to gas flow

Nonlinear instability and breakup of an annular liquid sheet has been modeled in this paper. The liquid sheet is considered to move axially and is exposed to co-flowing inner and outer gas streams. Also, the effect of outer gas swirl on sheet breakup has been studied. In the developed model a perturbation expansion method has been used with the initial magnitude of the disturbance as the perturbation parameter. This is a comprehensive model in that other geometries of planar sheet and a coaxial jet can be obtained as limiting cases of very large inner radius and inner radius equal to zero, respectively. In this temporal analysis, the effect of liquid Weber number, initial disturbance amplitude, inner gas-to-liquid velocity ratio, outer gas-to-liquid velocity ratio and outer gas swirl strength on the breakup time is investigated. The model is validated by comparison with earlier analytical studies for the limiting case of a planar sheet as well as with experimental data of sheet breakup length available in literature. It is shown that the linear theory cannot predict breakup of an annular sheet and the developed nonlinear model is necessary to accurately determine the breakup length. In the limiting case of a coaxial jet, results show that gas swirl destabilizes the jet, makes helical modes dominant compared to the axisymmetric mode and decreases jet breakup length. These results contradict earlier linear analyses and agree with experimental observations. For an annular sheet, it is found that gas flow hastens the sheet breakup process and shorter breakup lengths are obtained by increasing the inner and the outer gas velocity. Axially moving inner gas stream is more effective in disintegrating the annular sheet compared to axially moving outer gas stream. When both gas streams are moving axially, the liquid sheet breakup is quicker compared to that with any one gas stream. In the absence of outer gas swirl, the axisymmetric mode is the dominant instability mode. However, when outer gas flow has a swirl component higher helical modes become dominant. With increasing outer gas swirl strength, the maximum disturbance growth rate increases and the most unstable circumferential wave number increases resulting in a highly asymmetric sheet breakup with shorter breakup lengths and thinner ligaments.     

Structure development in curing of poly(phenylene sulfide)

The structure development during melt curing of poly(phenylene sulfide) (PPS) is reported. The changes in the structure were monitored using various characterization techniques such as differential scanning calorimetry, thermogravimetric analysis, infrared spectroscopy, and optical microscopy. It was observed that the thermal parameters such as melting point and heat of fusion are very sensitive to the structural changes and can be effectively used to monitor the curing process. The effect of curing environment was also investigated, and it was found that the rate of change of structure is considerably higher in air than in nitrogen. The results are discussed on the basis of the different mechanisms for curing of PPS.     

Crystallization of poly(phenylenesulfide)/amorphous polyamide blends: DSC and microscopic studies

Poly(phenylenesulfide) (PPS) is a high-performance engineering thermoplastic with exceptional thermal and chemical resistance. The results of crystallization behavior of blends of PPS with amorphous polyamide (PA) are presented. The melting and crystallization behavior was studied using differential scanning calorimetry (DSC), and the crystalline morphology was studied using optical microscopy. The results of thermal analysis indicate that the blends exhibit composition-dependent melting point depression. Optical microscopy studies showed the uniform distribution of amorphous nylon in PPS spherulites. The presence of amorphous nylon enhanced the growth rate compared to that for the neat polymer. The observed changes in the equilibrium melting point crystallization behavior, and spherulitic growth rate are explained.     

Crystallization and equilibrium melting behavior of PBT/PETG blends

The results of studies of equilibrium melting point and crystallization behavior of PBT/PETG blends are reported for the first time. A single composition‐dependent glass‐transition temperature is observed in the DSC studies. The isothermal crystallization studies of the blends indicate retardation in crystallization rate as evidenced by the increase in crystallization half time. The retardation in crystallization rate has been attributed to the miscibility in the molten state and the hindrance to the diffusion of crystallizable units. This assumption is further supported by the composition dependence of the crystallization half time. A composition‐dependent melting point depression has been observed which has been attributed to the possible thermodynamic and morphological effects. The interaction parameter calculated by analyzing equilibrium melting point depression shows composition‐dependent negative values confirming the miscibility of the systems. These results are in good agreement with our earlier results on mechanical and dynamic mechanical properties of PBT/PETG blends. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2439–2444, 1999