Madelung-Buckingham model as applied to the prediction of voltage, crystal volume changes, and ordering phenomena in spinel-type cathodes for lithium batteries

Using a Madelung-Buckingham model, we study Li(x)()Mn(2)O(4) and its fluorine-substituted analogue to compute their voltages, lattice volume changes, and ordering phenomena during charge/discharge. The interactions included are the long-range Coulombic, short-range electron-electron repulsion, and the van der Waals. The voltage of the fluorine-substituted spinel is found to be slightly less than that of the unsubstituted. However, the former undergoes a greater crystal volume change than the latter during intercalation and de-intercalation. Investigations of lithium sublattice ordering in this system indicates that during intercalation lithium starts filling exclusively into one sublattice until x = 0.5, and only from x = 0.5 the other sublattice is filled up to x = 1. The models are compared with quantum ab initio and experimental results.     

The crystal growth and perfection of 2,4,6-trinitrotoluene

Large crystals of TNT were grown from ethyl acetate solution by both temperature lowering and solvent evaporation. The perfection of crystals grown from seeds under carefully controlled conditions was generally higher than those prepared by uncontrolled solvent evaporation. Examination by X-ray topography revealed the crystals to have a characteristic growth induced defect structure comprising growth sectors and boundaries, growth banding, solvent inclusions and dislocations. Twins and stacking faults (SF) were also observed. Many of the defects noted in the topographs can be attributed to impurities. The influence of the highly anisotropic crystal structure on the nature of growth defects is discussed. A structural model proposed to explain twinning and SF formation is partially supported by topographic evidence.     

Strong enhancement of streaming current power by application of two phase flow

We show that the performance of a streaming-potential based microfluidic energy conversion system can be strongly enhanced by the use of two phase flow. Injection of gas bubbles into a liquid-filled channel increases both the maximum output power and the energy conversion efficiency. In single-phase systems the internal conduction current induced by the streaming potential limits the output power, whereas in a two-phase system the bubbles reduce this current and increase the power. In our system the addition of bubbles enhanced the maximum output power of the system by a factor of 74 and the efficiency of the system by a factor of 163 compared with single phase flow.     

Ocean forecasting in terrain-following coordinates: Formulation and skill assessment of the Regional Ocean Modeling System

Systematic improvements in algorithmic design of regional ocean circulation models have led to significant enhancement in simulation ability across a wide range of space/time scales and marine system types. As an example, we briefly review the Regional Ocean Modeling System, a member of a general class of three-dimensional, free-surface, terrain-following numerical models. Noteworthy characteristics of the ROMS computational kernel include: consistent temporal averaging of the barotropic mode to guarantee both exact conservation and constancy preservation properties for tracers; redefined barotropic pressure-gradient terms to account for local variations in the density field; vertical interpolation performed using conservative parabolic splines; and higher-order, quasi-monotone advection algorithms. Examples of quantitative skill assessment are shown for a tidally driven estuary, an ice-covered high-latitude sea, a wind- and buoyancy-forced continental shelf, and a mid-latitude ocean basin. The combination of moderate-order spatial approximations, enhanced conservation properties, and quasi-monotone advection produces both more robust and accurate, and less diffusive, solutions than those produced in earlier terrain-following ocean models. Together with advanced methods of data assimilation and novel observing system technologies, these capabilities constitute the necessary ingredients for multi-purpose regional ocean prediction systems.     

Investigation of the radical copolymerization and terpolymerization of maleic anhydride and norbornenes by an in situ 1H NMR analysis of kinetics and by the mercury method: Evidence for the lack of charge‐transfer‐complex propagation

The radical copolymerization of electron‐deficient maleic anhydride (MA) and electron‐rich norbornene (NB) derivatives with 2,2′‐azobis(isobutyronitrile) (AIBN) in dioxane‐d₈ has been monitored in situ by ¹H NMR spectroscopy with free induction decays recorded every 30 min at 60, 70, or 84 °C. The ratios of the monomer pairs were varied in some cases. The NB derivatives employed in this study included bicyclo[2.2.1]hept‐2‐ene (NB), t‐butyl 5‐norbornene‐2‐carboxylate, methyl 5‐norbornene‐2‐methyl‐2‐carboxylate, and ethyl tetracyclo[4.4.0.1^2,5.1^7,10]dodec‐3‐ene‐8‐carboxylate. Decomposition of AIBN, consumption of the monomers, feed ratios, endo/exo ratios, copolymer compositions, and copolymer yields were studied as a function of polymerization time. Furthermore, a homopolymerizable third monomer (t‐butyl methacrylate, methacrylic acid, t‐butyl acrylate, or acrylic acid) was added to the NB/MA 1/1 system, revealing that the methacrylic monomer polymerizes rapidly in the early stage and that the ratio of MA to NB in the terpolymer strongly deviates from 1/1. In contrast, however, the acrylic monomers are more uniformly incorporated into the polymer. Nevertheless, these studies indicate that MA and NB do not always behave as a pair in radical polymerization and disproves the commonly believed charge‐transfer mechanism. Electron‐deficient fumaronitrile was also included in the kinetics study. To further understand the copolymerization mechanism, MA and NB were competitively reacted with a cyclohexyl radical generated by the treatment of cyclohexylmercuric chloride with sodium borohydride (mercury method). A gas chromatographic analysis of the reaction mixtures has revealed that a cyclohexyl radical reacts with MA almost exclusively in competition and that the cyclohexyl adduct of MA essentially accounts for all the products in a mass balance experiment, eliminating a possibility of the formation of an adduct involving the MA–NB charge‐transfer complex. Thus, the participation of a charge‐transfer complex in the copolymerization of MA and NB cannot be important. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3521–3542, 2000     

Growth of the New Infrared Nonlinear Optical Crystal DCNP

This paper reports on the growth of 3-(1,1-dicyanothenyl)-1-phenyl-4,5-dihydro-1 H-pyrazole (DCNP) crystals in dimethylformamide. The effect of different solvents on the growth of DCNP has been investigated. Dimethylformamide was found to be a good solvent, Transparent DCNP single crystals were grown from this solvent. They are a promising infrared nonlinear material.