Robert P. Currier

Characterization of reaction intermediate aggregates in aniline oxidative polymerization at low proton concentration.

Aggregates of reaction intermediates form during the early stages of aniline oxidative polymerization whenever the initial mole ratio of proton concentration to aniline monomer concentration is low ([H(+)](0)/[An](0) <or= 1.0). Detailed characterization is carried out on those aggregates. The intermediate aggregates show a UV-Vis absorption peak at around 410 nm when dispersed in aqueous solution, whereas the peak is centered on 370 nm when dissolved in an organic solvent such as N-methylpyrrolidone. The electronic band gap decreases when the intermediates aggregate to form a solid, and thus, the absorption peak is red-shifted. Gel permeation chromatography (GPC) shows the aggregates contain a major low molecular weight peak with a long tail. The oligoanilines with low molecular weights consistently show a UV-Vis absorption peak at around 370 nm. Mass spectrometry confirms that the intermediate aggregates contain mainly a component with mass number 363 (M + H(+)), likely a tetramer. UV-Vis, GPC, mass spectrometry, NMR, FTIR, and XRD characterization results are presented and chemical structures for the tetramer are proposed. The major components of the intermediate aggregates are likely highly symmetric phenazine- and dihydrophenazine-containing structures. These particular organic compounds have not been identified before as intermediates. The aggregation and precipitation of the tetramers apparently stabilizes these intermediates. The aggregates are highly crystalline, as evidenced by powder X-ray diffraction. A new reaction mechanism for the formation of these intermediates is proposed.

Where Does Water Go During Hydraulic Fracturing

During hydraulic fracturing millions of gallons of water are typically injected at high pressure into deep shale formations. This water can be housed in fractures, within the shale matrix, and can potentially migrate beyond the shale formation via fractures and/or faults raising environmental concerns. We describe a generic framework for producing estimates of the volume available in fractures and undamaged shale matrix where water injected into a representative shale site could reside during hydraulic fracturing, and apply it to a representative site that incorporates available field data. The amount of water that can be stored in the fractures is estimated by calculating the volume of all the fractures associated with a discrete fracture network (DFN) based on real data and using probability theory to estimate the volume of smaller fractures that are below the lower cutoff for the fracture radius in the DFN. The amount of water stored in the matrix is estimated utilizing two distinct methods-one using a two-phase model at the pore-scale and the other using a single-phase model at the continuum scale. Based on these calculations, it appears that most of the water resides in the matrix with a lesser amount in the fractures.

High-pressure/low-temperature neutron scattering of gas inclusion compounds: Progress and prospects

Alternative energy resources such as hydrogen and methane gases are becoming increasingly important for the future economy. A major challenge for using hydrogen is to develop suitable materials to store it under a variety of conditions, which requires systematic studies of the structures, stability, and kinetics of various hydrogen-storing compounds. Neutron scattering is particularly useful for these studies. We have developed high-pressure/low-temperature gas/fluid cells in conjunction with neutron diffraction and inelastic neutron scattering instruments allowing in situ and real-time examination of gas uptake/release processes. We studied the formation of methane and hydrogen clathrates, a group of inclusion compounds consisting of frameworks of hydrogen-bonded H2O molecules with gas molecules trapped inside the cages. Our results reveal that clathrate can store up to four hydrogen molecules in each of its large cages with an intermolecular H2–H2 distance of only 2.93 Å. This distance is much shorter than that in the solid/metallic hydrogen (3.78 Å), suggesting a strong densification effect of the clathrate framework on the enclosed hydrogen molecules. The framework-pressurizing effect is striking and may exist in other inclusion compounds such as metal-organic frameworks (MOFs). Owing to the enormous variety and flexibility of their frameworks, inclusion compounds may offer superior properties for storage of hydrogen and/or hydrogen-rich molecules, relative to other types of compounds. We have investigated the hydrogen storage properties of two MOFs, Cu3[Co(CN)6]2 and Cu3(BTC)2 (BTC = benzenetricarboxylate), and our preliminary results demonstrate that the developed neutron-scattering techniques are equally well suited for studying MOFs and other inclusion compounds.

Plasma fluidized bed imaging and possible strong coupling effects

A plasma fluidized bed was constructed to study the physics of fluidized plasmas. The plasma fluidized bed is a unique system involving contact of hydrodynamically suspended micron-sized (and larger) particles with the current-carrying portion of a plasma. These particles become negatively charged and, under certain conditions, could possibly form a strongly coupled fluidized plasma. Using laser light scattering measurements, we have imaged particles and calculated a coupling parameter showing what could be strongly coupled effects superimposed on the hydrodynamic behavior of the fluidized bed systems. This system may provide an ideal means to experimentally explore the properties and dynamics of strongly coupled plasmas subjected to hydrodynamic shear forces.