Gas permeability in rubbery polyphosphazene membranes

The synthesis, characterization, and gas permeability of 10 new polyphosphazenes has been studied. Additionally, the first gas permeation data has been collected on hydrolytically unstable poly[bis-(chloro)phosphazene]. Gases used in this study include CO₂, CH₄, O₂, N₂, H₂, and Ar. CO₂ was the most permeable gas through any of the phosphazenes and a direct correlation between the T_g of the polymer and CO₂ transport was noted with permeability increasing with decreasing polymer T_g. To a lesser degree, permeability of all the other gases studied also yielded increases with decreasing polymer T_g. The trend observed for these new polymers was further supported by published data for other phosphazenes. Furthermore, permeability data for all gases were found to correlate to the gas condensability and the gas critical pressures, except for hydrogen, suggesting that the nature of the gas is also a significant factor for permeation through rubbery phosphazene membranes. Ideal separation factors () for the CO₂/H₂ and CO₂/CH₄ gas pairs were calculated. For CO₂/CH₄, no increase in was observed with decreasing T_g, however increases in were noted for the CO₂/H₂ pair.     

Polymer/silicate composites: new materials for subsurface permeable reactive barriers

Investigations were performed into the suitability of novel composites to serve as materials for subsurface permeable reactive barriers (PRBs). These new materials are Type I composites—they are preformed organic polymers embedded in an inorganic matrix without significant covalent bonding between the components. The required properties for these materials to function efficiently are: (1) a tunable water passing rate to approximate the hydraulic conductivity of the subsurface environment where the PRB will be placed, (2) sufficient mechanical strength (both wet and dry) to maintain barrier integrity, (3) the ability to incorporate selective metal sequestration agents so that they remain active—yet do not leach from the barrier, and (4) to be deployable through direct injection methods such that trenching is not needed. Additionally, there is a need to keep the technology as low cost as possible, while remaining reliable. Results recently obtained in our laboratory show that our materials, remarkably, exhibit all of these properties and show great promise as vadose zone deployable PRBs.     

Selective separation of minor actinides and lanthanides using aromatic dithiophosphinic and phosphinic acid derivatives

A new extractant for the separation of actinide(III) and lanthanide(III) cations, bis(o-trifluoromethylphenyl) phosphinic acid (2) was synthesized. The synthetic route employed mirrors one that was employed to produce the sulfur containing analog bis(o-trifluoromethylphenyl) dithiophosphinic acid (1). Classic radiochemical methods and absorbance spectroscopy were used to study the coordination chemistry of the Am-dithiophosphinic acid and Am-phosphinic acid complexes.     

Determination of the latent heat of fusion and solid fraction evolution of metals and alloys by an improved cooling curve analysis method

Journal of Thermal Analysis and Calorimetry - In this work, a new computer-aided cooling curve analysis method (CA-CCA) called metal/mold energy balance method (MEB) is presented. Its originality...     

Synthesis and Characterization of Mixed-Substituent P- n -Propyl-N-trimethylsilylphosphoranimines

One approach to the synthesis of polyphosphazenes is the condensation polymerization of phosphoranimines. In this work, several novel P-n-propyl-N-trimethylsilylphosphoranimines have been synthesized and characterized. Modifications to the literature synthetic routes were required to obtain the precursor phosphines. The N-trimethylsilylphosphoranimines were obtained though oxidation of the phosphine with bromine and then subsequent nucleophilic displacement using lithium phenoxide. These phosphoranimines were stable for long periods of time under dry inert conditions. NMR analyses revealed complex splitting patterns beyond typical coupling due to the stereocenter at phosphorus. We report several approaches to the n-propyl containing phosphines and phosphoranimines.