Direct Formation and Structural Characterization of Electride C12A7.

Ca12Al14O33 (C12A7 or Mayenite) is a material whose caged clathrate structure and occluded anionic species leads to significant functionality. The creation of occluded anionic vacancies leads to the injection of localized electrons at the center of the cage, converting the wide band gap insulator to a semi- or metallic conducting material. The conversion to the electride historically requires the synthesis of oxy-C12A7, consolidation, and then reduction to introduce anionic vacancies. This report develops and characterizes an electride formation procedure from three starting points: unconsolidated oxy-C12A7, heterogenous solid-state reactants (CaCO3 and Al2O3), and homogenous non-carbonaceous polymer assisted sol-gel reactants. Electride-C12A7 formation is observed in a vacuum furnace where the reactants are in direct contact with a carbon source. Process time and temperature-dependent structural characterization provides insight into the source of high temperature C12A7 stability, the mechanism of anionic vacancy formation, and the magnitude of ultimate conductivity that cannot be explained by current reduction theories. A new theory is presented where mixed O- and C-occupied cages lead to high temperature stability, oxidation of C species creates anionic vacancies, and an equilibrium between the reducing power of the electride-C12A7 and of the C species leads to the ultimate conductivity achieved by the process. This represents a shift in understanding of the carbonaceous reduction process and the first report of high purity electride-C12A7 formation from heterogenous solid-state reactants and homogenous non-carbonaceous polymer assisted sol-gel reactants.

Visualization of conformational changes of linear short-chain polyethylenes under shear and elongational flows.

We have performed nonequilibrium molecular dynamic simulations of the linear short-chain polyethylene liquids C(24)H(50), C(50)H(102), C(78)H(158), and C(128)H(258) under homogenous shear and elongational flows. We present visualizations of the molecular structure of each of the four liquids under shear and elongation, and compare them with their equilibrium static structures. These graphics provide a structural understanding of the various statistical measures that have been used in the literature to characterize the change in chain conformation as a function of strain rate and chain length. Moreover, these graphics allow a visualization of the inherent chain dynamics and orientation induced by shear and elongational flows. We discuss the molecular-level mechanisms apparent in the graphics.

A validation of the p-SLLOD equations of motion for homogeneous steady-state flows.

A validation of the p-SLLOD equations of motion for nonequilibrium molecular dynamics simulation under homogeneous steady-state flow is presented. We demonstrate that these equations generate the correct center-of-mass trajectory of the system, are completely compatible with (and derivable from) Hamiltonian dynamics, satisfy an appropriate energy balance, and require no fictitious external force to generate the required homogeneous flow. It is also shown that no rigorous derivation of the SLLOD equations exists to date.

Rheological and structural studies of linear polyethylene melts under planar elongational flow using nonequilibrium molecular dynamics simulations.

We present various rheological and structural properties of three polyethylene liquids, C50H102, C78H158, and C128H258, using nonequilibrium molecular dynamics simulations of planar elongational flow. All three melts display tension-thinning behavior of both elongational viscosities, eta1 and eta2. This tension thinning appears to follow the power law with respect to the elongation rate, i.e., eta approximately epsilon(b), where the exponent b is shown to be approximately -0.4 for eta1 and eta2. More specifically, b of eta1 is shown to be slightly larger than that of eta2 and to increase in magnitude with the chain length, while b of eta2 appeared to be independent of the chain length. We also investigated separately the contribution of each mode to the two elongational viscosities. For all three liquids, the intermolecular Lennard-Jones (LJ), intramolecular LJ, and bond-stretching modes make positive contributions to both eta1 and eta2, while the bond-torsional and bond-bending modes make negative contributions to both eta1 and eta2. The contribution of each of the five modes decreases in magnitude with increasing elongation rate. The hydrostatic pressure shows a clear minimum at a certain elongation rate for each liquid, and the elongation rate at which the minimum occurs appears to increase with the chain length. The behavior of the hydrostatic pressure with respect to the elongation rate is shown to correlate with the intermolecular LJ energy from a microscopic viewpoint. On the other hand, R(ete)2 and R(g)2 appear to be correlated with the intramolecular LJ energy. The study of the effect of the elongational field on the conformation tensor c shows that the degree of increase of tr(c)-3 with the elongation rate becomes stronger as the chain length increases. Also, the well-known linear reaction between sigma and c does not seem to be satisfactory. It seems that a simple relation between sigma and c would not be valid, in general, for arbitrary flows.

Structure formation under steady-state isothermal planar elongational flow of n-eicosane: a comparison between simulation and experiment.

We use nonequilibrium molecular dynamics simulations to investigate the structural properties of an oriented melt of n-eicosane under steady-state planar elongational flow. The flow-induced structure was evaluated using the structure factor s(k) taken as the Fourier transform of the total pair correlation function g(r). We found that the equilibrium liquid structure factor is in excellent agreement with the one determined via x-ray diffraction. Moreover, a new x-ray diffraction experiment has been performed on a crystalline n-eicosane sample. The resulting intramolecular contribution to the structure factor was found to be in very good agreement with the simulated one at a high elongation rate, indicating the existence of a possible crystalline precursor structure.

Rheological and structural studies of liquid decane, hexadecane, and tetracosane under planar elongational flow using nonequilibrium molecular-dynamics simulations.

We report for the first time rheological and structural properties of liquid decane, hexadecane, and tetracosane using nonequilibrium molecular-dynamics (NEMD) simulations under planar elongational flow (PEF). The underlying NEMD algorithm employed is the so-called p-SLLOD algorithm [C. Baig, B. J. Edwards, D. J. Keffer, and H. D. Cochran, J. Chem. Phys. 122, 114103 (2005)]. Two elongational viscosities are measured, and they are shown not to be equal to each other, indicating two independent viscometric functions in PEF. With an appropriate definition, it is observed that the two elongational viscosities converge to each other at very low elongation rates, i.e., in the Newtonian regime. For all three alkanes, tension-thinning behavior is observed. At high elongation rates, chains appear to be fully stretched. This is supported by the result of the mean-square end-to-end distance of chains (R(ete2)) and the mean-square radius of gyration of chains (R(g2)), and further supported by the result of the intramolecular Lennard-Jones (LJ) potential energy. It is also observed that (R(ete2)) and (R(g2)) show a different trend as a function of strain rate from those in shear flow: after reaching a plateau value, (R(ete2)) and (R(g2)) are found to increase further as elongation rate increases. A minimum in the hydrostatic pressure is observed for hexadecane and tetracosane at about epsilon(msigma2/epsilon)1/2=0.02. This phenomenon is shown to be associated with the intermolecular LJ potential energy. The bond-bending and torsional energies display similar trends, but a different behavior is observed for the bond-stretching energy. An important observation common in these three bonded-intramolecular interactions is that all three modes are suppressed to a small value at high elongation rates. We conjecture that a liquid-crystal-like, nematic structure is present in these systems at high elongation rates, which is characterized by a strong chain alignment with a fully stretched conformation.

A proper approach for nonequilibrium molecular dynamics simulations of planar elongational flow.

We present nonequilibrium molecular dynamics simulations of planar elongational flow (PEF) by an algorithm proposed by Tuckerman et al. [J. Chem. Phys. 106, 5615 (1997)] and theoretically elaborated by Edwards and Dressler [J. Non-Newtonian, Fluid Mech. 96, 163 (2001)], which we shall call the proper-SLLOD algorithm, or p-SLLOD for short. [For background on names of algorithms see W. G. Hoover, D. J. Evans, R. B. Hickman, A. J. C. Ladd, W. T. Ashurst, and B. Moran, Phys. Rev. A 22, 1690 (1980) and D. J. Evans and G. P. Morriss, Phys. Rev. A 30, 1528 (1984).] We show that there are two sources for the exponential growth in PEF of the total linear momentum of the system in the contracting direction, which has been previously observed using the so-called SLLOD algorithm. The first comes from the SLLOD algorithm itself, and the second from the implementation of the Kraynik and Reinelt [Int. J. Multiphase Flow 18, 1045 (1992)] boundary conditions. Using the p-SLLOD algorithm (to eliminate the first source) implemented with our simulation strategy (to eliminate the second) in PEF simulations, we no longer observe the exponential growth. By analyzing the equations of motion, we also demonstrate that both the SLLOD and the DOLLS algorithms are intrinsically unsuitable for representing a nonequilibrium system with elongational flow. However, the p-SLLOD algorithm has a rigorously canonical structure in laboratory phase space, and thus can represent a nonequilibrium system not only for elongational flow but also for a general flow.

Behavior of oil droplets on an electrified solid metal surface immersed in ionic surfactant solutions.

The present study investigates the change in the shape of oil droplets immersed in an ionic surfactant solution when the droplets are in contact with metal surfaces to which an electrical potential is applied. The three-phase system of aqueous solution-oil-steel was subjected to low-voltage electric potentials, which resulted in sometimes dramatic changes in droplet shape and wetting. This electric potential was applied to the conductive steel surface directly, and the counter electrode was immersed in the solution. Changes in both the shape and wetting extent of hexadecane and phenylmethyl polysiloxane were observed for voltages between +/-3.0 V in both sodium dodecyl sulfate and cetyl trimethylammonium bromide solutions. The droplets' behavior was opposite to what would be expected for traditional electrowetting. In one instance, hexadecane droplets in sodium dodecyl sulfate solutions with a voltage of -3.0 V, a rapid and repeating droplet elongation and detachment was observed. Additionally, the impact of the observed phenomena on electrowetting enhanced ultrasonication is presented to demonstrate the potential improvements in industrial ultrasonic cleaning processes. The observations lead to the possibility of employing simple electrowetting techniques in the removal of oil from metal surfaces in a manner that could greatly improve the environmental and economic performance of aqueous cleaning techniques.

Thermodynamic method for prediction of surfactant-modified oil droplet contact angle.

A model applying surfactant self-assembly theory and classical thermodynamics has been developed to aid in the prediction of solid surface cleaning by aqueous surfactant solutions. Information gained from a combination of surfactant self-assembly behavior and cleaning system parameters, such as oil species, surfactant type, temperature, alkalinity, and solid surface type has been shown to provide insight into surface cleaning. The model combines minimization of free energy, pertinent component distribution mechanisms, and surfactant self-assembly processes to provide a methodology for the predicting of oil droplet contact angles. Such predictive capabilities will allow for the development of beneficial environmental and economic changes to industrial and commercial surface cleaning and degreasing processes. Results from the model will be compared to experimental data to verify the capability of the theory to account for the effect of solutions parameters on oil droplet behavior. The model, while approximate in nature, has shown a remarkable quantitative predictive ability.