Diffusion from sessile droplets through membranes

We analyze diffusion from a periodic array of hemispherical droplets through a membrane. We find that the multiple sources do not interact strongly, even when the droplets are closely spaced, so that the flux through the membrane appears nearly additive.     

Anionic polymerization of star-shaped nylon 6 with a trifunctional initiator

The anionic polymerization of ?-caprolactam (CLM) has been shown to proceed at high reaction rate when catalyzed by metallic lactamates and initiated by acyllactams. The role of initiator and catalyst concentration on the process of ?-caprolactam anionic polymerization has been explored, with the aim of selecting the most suitable experimental conditions for reaction injection molding (RIM). The overall polymerization rates and physical properties for reaction injection molding of star-shaped nylon 6 homopolymer have been studied by the quasi-adiabatic process. In order to model the actual rapid molding conditions, time vs. temperature reaction profiles were measured, and the relative rates of polymerization subsequently determined from these data.     

Variational extension of the mean spherical approximation to arbitrary dimensions

We generalize a variational principle for the mean spherical approximation for a system of charged hard spheres in 3D to arbitrary dimensions. We first construct a free energy variational trial function from the Debye-Hückel excess charging internal energy at a finite concentration and an entropy obtained at the zero-concentration limit by thermodynamic integration. In three dimensions the minimization of this expression with respect to the screening parameter leads to the mean spherical approximation, usually obtained by solution of the Ornstein-Zernike equation. This procedure, which interpolates naturally between the zero concentration/coupling limit and the high-concentration/ coupling limit, is extended to arbitrary dimensions. We conjecture that this result is also equivalent to the MSA as originally defined, although a technical proof of this point is left for the future. The Onsager limitT ΔS ^MSA /ΔE ^MSA → 0 for infinite concentration/coupling is satisfied for all d ≠ 2, while ford=2 this limit is 1. On leave from Department of Physics, University of Puerto Rico, Mayagüez Campus, Mayagüez, Puerto Rico, 00681.     

Thermodynamic characterization of interpenetrating polymer networks of poly (carbonate-urethane) and poly (methyl methacrylate)

Crosslinked poly (methyl methacrylate) and poly (carbonate-urethane) as well as full interpenetrating network on their base (IPN) were characterized by precise heat capacity measurements in the temperature interval 1.2–150 K. As judged by the positive sign of the excess Gibbs free energy in the whole temperature interval above 30 K, the apparently single-phase state of IPN is thermodynamically unstable; however, its kinetic stability is ensured by permanent chamical crosslinks prohibiting the incipient phase separation. © 1994 John Wiley & Sons, Inc.     

Hybrid inorganic/organic interpenetrating polymer networks based on zeolite 13x and polystyrene

A hybrid inorganic/organic interpenetrating polymer network (IPN) of a three-dimensional network structure zeolite crystal (13X, powder) and crosslinked or linear polystyrene (PS) was prepared and characterized by differential scanning calorimetry (DSC), solid-state¹³C-NMR, and scanning electron microscopy (SEM). The size and shape of the crystalline zeolite particles were revealed on SEM micrographs in both the pure zeolite and the IPNs. Solubility tests and the results of DSC with solid-state ¹³C-NMR confirm that some organic PS chains are incorporated within the internal three-dimensional channels of the zeolite particles. We speculate that the internal PS chains may adopt an extended “one-dimensional” conformation and exhibit no bulk polymer glass transition. These novel hybrid inorganic/organic IPNs are a new kind of IPN structure. © 1995 John Wiley & Sons, Inc.     

BIOLOGICAL ACTIVITIES OF PHTHALOCYANINES-X. SYNTHESES AND ANALYSES OF SULFONATED PHTHALOCYANINES

Abstract— Synthetic methods to obtain selectively sulfonated metallo phthalocyanines are compared. Both condensation and direct sulfonation procedures lead to mixtures of mono- to tetrasulfonated products which are resolved by reverse phase liquid chromatography in buffered aqueous-methanol. The proportion of sulfonated derivatives is examined as a function of the starting reagents in the case of the condensation method, and as a function of the temperature and reaction time in the case of the direct sulfonation procedure. The number of sulfonate groups per phthalocyanine molecule is determined by oxidative degradation of the phthalocyanine ring followed by quantitative chromatographic analysis of the sulfophthalamide and phthalamide fragments.