Two classes of quasi-steady-state model reductions for stochastic kinetics

The quasi-steady-state approximation (QSSA) is a model reduction technique used to remove highly reactive species from deterministic models of reaction mechanisms. In many reaction networks the highly reactive intermediates (QSSA species) have populations small enough to require a stochastic representation. In this work we apply singular perturbation analysis to remove the QSSA species from the chemical master equation for two classes of problems. The first class occurs in reaction networks where all the species have small populations and the QSSA species sample zero the majority of the time. The perturbation analysis provides a reduced master equation in which the highly reactive species can sample only zero, and are effectively removed from the model. The reduced master equation can be sampled with the Gillespie algorithm. This first stochastic QSSA reduction is applied to several example reaction mechanisms (including Michaelis-Menten kinetics) [Biochem. Z. 49, 333 (1913)]. A general framework for applying the first QSSA reduction technique to new reaction mechanisms is derived. The second class of QSSA model reductions is derived for reaction networks where non-QSSA species have large populations and QSSA species numbers are small and stochastic. We derive this second QSSA reduction from a combination of singular perturbation analysis and the Omega expansion. In some cases the reduced mechanisms and reaction rates from these two stochastic QSSA models and the classical deterministic QSSA reduction are equivalent; however, this is not usually the case

Stochastic simulation of catalytic surface reactions in the fast diffusion limit

The master equation of a lattice gas reaction tracks the probability of visiting all spatial configurations. The large number of unique spatial configurations on a lattice renders master equation simulations infeasible for even small lattices. In this work, a reduced master equation is derived for the probability distribution of the coverages in the infinite diffusion limit. This derivation justifies the widely used assumption that the adlayer is in equilibrium for the current coverages and temperature when all reactants are highly mobile. Given the reduced master equation, two novel and efficient simulation methods of lattice gas reactions in the infinite diffusion limit are derived. The first method involves solving the reduced master equation directly for small lattices, which is intractable in configuration space. The second method involves reducing the master equation further in the large lattice limit to a set of differential equations that tracks only the species coverages. Solution of the reduced master equation and differential equations requires information that can be obtained through short, diffusion-only kinetic Monte Carlo simulation runs at each coverage. These simulations need to be run only once because the data can be stored and used for simulations with any set of kinetic parameters, gas-phase concentrations, and initial conditions. An idealized CO oxidation reaction mechanism with strong lateral interactions is used as an example system for demonstrating the reduced master equation and deterministic simulation techniques

The stochastic quasi-steady-state assumption: Reducing the model but not the noise

Highly reactive species at small copy numbers play an important role in many biological reaction networks. We have described previously how these species can be removed from reaction networks using stochastic quasi-steady-state singular perturbation analysis (sQSPA). In this paper we apply sQSPA to three published biological models: the pap operon regulation, a biochemical oscillator, and an intracellular viral infection. These examples demonstrate three different potential benefits of sQSPA. First, rare state probabilities can be accurately estimated from simulation. Second, the method typically results in fewer and better scaled parameters that can be more readily estimated from experiments. Finally, the simulation time can be significantly reduced without sacrificing the accuracy of the solution

Corrosion properties of chromia based eco - friendly coatings on mild steel

Ceramic nanocrystalline coatings of chromium oxide (III) on steel S235JRH-1.0038 (EN 10025-1) were prepared using the liquid precursor plasma spraying (LPPS) method from ammonia dichromate (VI). Their structure and anti – corrosion properties were compared to the standard chromium oxide (III) coating prepared by thermal spraying. The newly prepared coatings had very high adhesion and minimal porosity. Anticorrosion properties were characterized by the means of the electrochemical impedance spectroscopy (EIS), measuring the charge transfer resistance Rct and capacitance of electrical double layer CPEdl in the 0,5 mol/l NaCl. Coatings of Cr2 O3 prepared by the LPPS method showed unambiguously improved anti - corrosion properties

Bond strength of plasma sprayed ceramic coatings on the phosphated steels

In the presented work, results of adhesion measurements for different systems of steel sheet-phosphate interlayer-ceramiccoating are described. The interlayers were produced by zinc phosphating; alumina, olivine and zirconiasilica-alumina (e.g. eucor) coatings were deposited by water stabilized plasma torch WSP®. However, successful application of the WSP technique depends on the choice of correct deposition parameters preserving the hydrated phosphates from thermal destruction by the molten ceramic particles. For the adhesion measurement ISO 4624standardized test was used. Corrosion resistivity was measured by polarisation resistance and free corrosion potential in 3 % NaCl solution. Key words

Boronized steels with corundum-baddeleyite coatings

The paper describes preparation and properties of anti-corrosion and anti-abrasive coatings from corundum-baddeleyite ceramics deposited on surface of low-carbon boronized steel S235JRH-1.0038 (EN 10025-1) by plasma spraying method. Adhesive interlayers Fe2B reaches bond strength of up to 20 MPa in the pull-off tests, the ZrO2 - Al2O3 - SiO2 coatings have a value of fracture adhesion of 4 - 6 MPa. Hardness of these ceramic coatings on steel is as high as 1 800 HV100 and its polarization resistance is 1 600 Ω/cm2 to 4 000 Ω/cm2

Thermal stability of phosphate coatings on steel

The work was validated thermal stability of zinc, manganese and tri-cations phosphate coatings on steel, made from commercial phosphating bath type Pragofos. Thermogravimetric data dehydration of scholzite, phosphophylite and hureaulite coatings in the temperature range 160 °C – 400 °C define the conditions for applying paints with higher firing temperature or thermal spraying ceramic coatings

Renewables 2010: Global Status Report

This report describes economic trends in building the capacity of renewable energy in several countries

Intelligence within BAOR and NATO's Northern Army Group

During the Cold War the UK's principal military role was its commitment to the North Atlantic Treaty Organisation (NATO) through the British Army of the Rhine (BAOR), together with wartime command of NATO's Northern Army Group. The possibility of a surprise attack by the numerically superior Warsaw Pact forces ensured that great importance was attached to intelligence, warning and rapid mobilisation. As yet we know very little about the intelligence dimension of BAOR and its interface with NATO allies. This article attempts to address these neglected issues, ending with the impact of the 1973 Yom Kippur War upon NATO thinking about warning and surprise in the mid-1970s. It concludes that the arrangements made by Whitehall for support to BAOR from national assets during crisis or transition to war were - at best - improbable. Accordingly, over the years, BAOR developed its own unique assets in the realm of both intelligence collection and special operations in order to prepare for the possible outbreak of conflict