Kinetic model for hydrocarbon-assisted particulate boron combustion

A kinetic model is presented to describe the high temperature (1800 K < T < 3000 K) surface oxidation of particulate boron in a hydrocarbon combustion environment. The model includes a homogeneous gas-phase B/O/H/C oxidation mechanism consisting of 19 chemical species and 58 forward and reverse elementary reactions, multi-component gas-phase diffusion, and a heterogeneous surface oxidation mechanism consisting of ‘elementary’ adsorption and desorption reaction steps. Thermochemical and kinetic parameters for the surface reactions are estimated from available experimental data and/or elementary transition state arguments. The kinetic processes are treated using a generalized kinetics code, with embedded sensitivity analysis, for the combustion of a one-dimensional (particle radius), spherical particle. Model results are presented for the oxidation of a 200 μm boron particle in a JP-4/air mixture at ambient temperatures of 1400 K and 2000 K. These results include temperature and gas-phase species profiles as a function of radial distance and particle burning rates. © 1994 John Wiley & Sons, Inc.     

Combustion of bimodal nano/micron-sized aluminum particle dust in air

The combustion of bimodal nano/micron-sized aluminum particles with air is studied both analytically and experimentally in a well-characterized laminar particle-laden flow. Experimentally, an apparatus capable of producing Bunsen-type premixed flames was constructed to investigate the flame characteristics of bimodal-particle/air mixtures. The flame speed is positively affected by increasing the mass fraction of nano particles in the fuel formulation despite the lower flame luminosity and thicker flame zone. Theoretically, the flames are assumed to consist of several different regimes for fuel-lean mixture, including the preheat, flame, and post flame zones. The flame speed and temperature distribution are derived by solving the energy equation in each regime and matching the temperature and heat flux at the interfacial boundaries. The analysis allows for the investigation of the effects of particle composition and equivalence ratio on the burning characteristics of aluminum-particle/air mixtures. Reasonable agreement between theoretical results and experimental data was obtained in terms of flame speed. The flame structure of a bimodal particle dust cloud may display either an overlapping or a separated configuration, depending on the combustion properties of aluminum particles at different scales. At low percentages of nano particles in the fuel formulation, the flame exhibits a separated spatial structure with a wider flame regime. At higher nano-particle loadings, overlapping flame configurations are observed.     

DYNGA: a general purpose QM-MM-MD program. I. Application to water

We present a general purpose QM-MM-MD engine (DYNGA) designed to test alternative hybrid Hamiltonians geared towards the treatment of problems of interest in structural biology including the use of experimental data constraints. In this first presentation we use DYNGA to explore the behaviour of a traditional QM-MM approach in the treatment of the water—water interaction. We find the potential energy hypersurface for the water dimer computed with the HF 4–31G*/TIP3P hybrid Hamiltonian tends to be too flat. We also explore the effect of using traditional QM-MM techniques on proton wires and conclude there is a need for improvement, possibly addressed by using polarizable force fields.     

PAST AND FUTURE MANAGEMENT OF A COLLAPSED FISHERY: THE BAY OF BISCAY ANCHOVY

Abstract We analyze the efficiency of the international management of the Bay of Biscay anchovy. While a sharing agreement between France and Spain has been in place since 1992, the fish stock collapsed in 2005 and the fishery closed from 2005 to spring 2010. We consider differences in production technologies between both countries and calibrate our model using data from 1987 to 2009. Our results suggest two sources of rent dissipation under the existing sharing agreement: inefficient quota allocation and production inefficiencies due to inflexible national regulations. We discuss several alternatives to improve management.     

Flame propagation of nano/micron-sized aluminum particles and ice (ALICE) mixtures

Flame propagation of aluminum–ice (ALICE) mixtures is studied theoretically and experimentally. Both a mono distribution of nano aluminum particles and a bimodal distribution of nano- and micron-sized aluminum particles are considered over a pressure range of 1–10 MPa. A multi-zone theoretical framework is established to predict the burning rate and temperature distribution by solving the energy equation in each zone and matching the temperature and heat flux at the interfacial boundaries. The burning rates are measured experimentally by burning aluminum–ice strands in a constant-volume vessel. For stoichiometric ALICE mixtures with 80 nm particles, the burning rate shows a pressure dependence of r_b = aPⁿ, with an exponent of 0.33. If a portion of 80 nm particles is replaced with 5 and 20 μm particles, the burning rate is not significantly affected for a loading density up to 15–25% and decreases significantly beyond this value. The flame thickness of a bimodal-particle mixture is greater than its counterpart of a mono-dispersed particle mixture. The theoretical and experimental results support the hypothesis that the combustion of aluminum–ice mixtures is controlled by diffusion processes across the oxide layers of particles.     

ConFlo III - an interface for high precision delta(13)C and delta(15)N analysis with an extended dynamic range

A newly developed interface coupling a CHN combustion device (elemental analyser 'EA') to an isotope ratio mass spectrometer is described and evaluated. The purpose of the device is to extend the dynamic range of delta(13)C and delta(15)N analysis from less than 2 orders of magnitude to more than 3 orders of magnitude. Carbon isotope ratio measurements of atropine as a model compound have been performed analysing between 1 μg to 5 mg C with acceptable to excellent precision (0.6 to 0.06 per thousand, delta-notation). The correction due to the blank signal is critical for sample amounts smaller than 4 μg C. The maximum sample weight is determined by the combustion capacity of the EA. Larger sample amounts are measured using dilution of a small part of the EA effluent with helium. The dilution mechanism works virtually free of isotope fractionation. Copyright 1999 John Wiley & Sons, Ltd.     

Dependence of flame propagation on pressure and pressurizing gas for an Al/CuO nanoscale thermite

The pressure dependence of flame propagation in an Al/CuO nanoscale thermite was studied. Experiments were performed by loosely packing the Al/CuO mixture in an instrumented burn tube, which was placed in a large volume, constant pressure chamber with optical windows. A high-speed camera was used to take photographic data, and six pressure transducers equally spaced along the length of the burn tube were used to measure the local transient pressure. Ambient pressures were varied between 0 and 15 MPa, and three different pressurizing gases were used: argon, helium, and nitrogen. Three modes of propagation were observed. The pressure at which the mode of propagation changed was similar for argon and nitrogen, however, when pressurized with helium, transition occurred at lower pressures. In the low-pressure regime (0–2 MPa) a constant velocity mode with speeds on the order of 1000 m/s was observed. In this region, a convective mode of propagation was dominant. An accelerating regime was observed for a pressure range of approximately 2–5 MPa in argon and nitrogen, with speeds ranging from 100 to 800 m/s. In helium, however, if an accelerating region existed it occurred over a narrow pressure range which was not observed in the present experiments. An oscillating regime was observed in all three gases, in a pressure range of 5–9 MPa for argon and nitrogen, and a range of 2–4 MPa for helium. Velocities in this region are bimodal, and differ by orders of magnitude, suggesting that the propagation mechanism was oscillating between convective and conductive. At relatively high ambient pressures, a constant velocity mode with speeds on the order of 1 m/s was observed for all three gases. The conductive mode of propagation was likely dominant in this region.     

The effect of stoichiometry on the combustion behavior of a nanoscale Al/MoO3 thermite

The effect of stoichiometry on the combustion behavior of the nanoscale aluminum molybdenum trioxide (nAl/MoO₃) thermite was studied in a burn tube experiment by characterizing the propagation velocity and pressure output of the reaction. Changing the stoichiometry affects the combustion through changes in the product temperature, phase, and composition. The mixture ratios of the composites were varied over an extremely wide range (5% nAl (95% MoO₃)–90% nAl (10% MoO₃)). Results revealed three separate combustion regimes: a steady high speed propagation (100 to 1000 m/s) from approximately 10% to 65% nAl, an oscillating and accelerating wave near 70% nAl, and a steady-slow speed propagation (0.1–1 m/s) from approximately 75% to 85% nAl. Propagation was observed to fail both <10% nAl and >85% nAl. This is the first known observation of such limits for a nanoscale thermite in a tube geometry. The instrumented tube tests revealed peak pressures over 8 MPa near stoichiometric conditions in the steady high speed propagation region, no measurable pressure rise at low speed propagation, and building pressures for accelerating waves. The results suggest the propagation mode to be a supersonic convective wave for near stoichiometric mixtures and a conductive deflagration for extremely fuel-rich mixtures. The implications of these results for microscale combustion applications are discussed.     

Abelian categories of modules over a (lax) monoidal functor

Crane and Yetter (Deformations of (bi)tensor categories, Cahier de Topologie et Géometrie Differentielle Catégorique, 1998) introduced a deformation theory for monoidal categories. The related deformation theory for monoidal functors introduced by Yetter (in: E. Getzler, M. Kapranov (Eds.), Higher Category Theory, American Mathematical Society Contemporary Mathematics, Vol. 230, American Mathematical Society, Providence, RI, 1998, pp. 117-134.) is a proper generalization of Gerstenhaber's deformation theory for associative algebras (Ann. Math. 78(2) (1963) 267; 79(1) (1964) 59; in: M. Hazewinkel, M. Gerstenhaber (Eds.), Deformation Theory of Algebras and Structure and Applications, Kluwer, Dordrecht, 1988, pp. 11-264). In the present paper we solidify the analogy between lax monoidal functors and associative algebras by showing that under suitable conditions, categories of functors with an action of a lax monoidal functor are abelian categories. The deformation complex of a monoidal functor is generalized to an analogue of the Hochschild complex with coefficients in a bimodule, and the deformation complex of a monoidal natural transformation is shown to be a special case. It is shown further that the cohomology of a monoidal functor F with coefficients in an F,F-bimodule is given by right derived functors.