Structural analyses of blended Nafion/PVDF electrospun nanofibers.

A new type of polymer blend, prepared by electrospinning nanofibers containing the immiscible polymers polyvinylidene fluoride (PVDF, 10 wt%) and Nafion® perfluorosulfonic acid (90 wt%), has been characterized experimentally. The internal nanofiber morphology is unique and unlike a normal blend, with individual phase-separated and randomly distributed fibrils of Nafion and PVDF (∼2-7 nm in diameter) that are bundled together and aligned in the fiber axis direction (where the fiber diameter is ∼500 nm). This morphology is retained when fiber mats are hot-pressed into dense films. The physicochemical properties of the electrospun blended fibers are also highly unusual and unanticipated. As shown in this study, each polymer component influences the thermal and structural behavior of the other, especially in the dry state. Thus, dry composite polymer mats and membranes exhibit properties and attributes that are not observed for either pure PVDF or pure Nafion. Experimental results indicate that: (i) PVDF imparts conformational constraints on the polytetrafluoroethylene (PTFE) backbone chains of Nafion, resulting in an increased 21 helical conformation that effects Nafion's water uptake and thermal properties; and (ii) dipole-dipole interactions between PVDF polymer chains and Nafion make the ß-phase polymorph of PVDF much more stable at elevated temperatures. Such "reciprocal templating" in electrospun fibers may not be unique to Nafion and PVDF, thus the procedure represents a new method of creating nanostructured multi-component polymer materials with innovative features.

A transient model of mass transfer and kinetics in a passive vapor sampler.

A transient model of vapor contaminant diffusion and homogeneous reaction in a two-compartment passive sampler was formulated. The mathematical analysis considered finite reaction kinetics, bulk air boundary-layer effects, and the solubility of the vapor contaminant in the liquid absorbing/reacting medium. The model was evaluated using experimentally measured Cl2 uptake rates in a series of samplers of different dimensions containing a 0.1% aqueous sulfamic acid solution in the absorbing medium chamber. The theory predicts accurately the effects of sampler diameter, stagnant air chamber path length, and sampler orientation with respect to the flowing air on Cl2 uptake, with an average error of less than 10%. Chlorine uptake in a 33-mm diameter sampler with a 10.8-mm path length was found to be essentially independent of wind direction and varied by approximately 23% for wind speeds ranging from 5.1 to 203 cm s-1 (10-400 ft min-1). Calculations show that the sampler is sensitive to wind speed partly because of the Cl2 hydrolysis reaction, which produces HOCl and drops the vapor phase concentration of chlorine to near zero at the stagnant air/absorbing medium chamber interface, regardless of the rate of homogeneous reaction between HOCl and sulfamate anions. If the solubility of the vapor contaminant in the liquid absorbing medium were to obey Henry's Law (no hydrolysis reaction) and the homogeneous trapping reaction were sufficiently slow, then model calculations show that contaminant uptake could be controlled solely by reaction kinetics, although the sampling rates would be lower than those observed and predicted for the Cl2 case.