Application of the Tris(acetylacetonato)iron(III)/(II) Redox Couple in p‐Type Dye‐Sensitized Solar Cells

An electrolyte based on the tris(acetylacetonato)iron(III)/(II) redox couple ([Fe(acac)₃]^0/1?) was developed for p‐type dye‐sensitized solar cells (DSSCs). Introduction of a NiO blocking layer on the working electrode and the use of chenodeoxycholic acid in the electrolyte enhanced device performance by improving the photocurrent. Devices containing [Fe(acac)₃]^0/1? and a perylene–thiophene–triphenylamine sensitizer (PMI–6T–TPA) have the highest reported short‐circuit current (J_SC=7.65 mA cm^?2), and energy conversion efficiency (2.51 %) for p‐type DSSCs coupled with a fill factor of 0.51 and an open‐circuit voltage V_OC=645 mV. Measurement of the kinetics of dye regeneration by the redox mediator revealed that the process is diffusion limited as the dye‐regeneration rate constant (1.7×10⁸ M ^?1 s^?1) is very close to the maximum theoretical rate constant of 3.3×10⁸ M ^?1 s^?1. Consequently, a very high dye‐regeneration yield (>99 %) could be calculated for these devices.     

Numerical study of the metal vapour transport in tungsten inert-gas welding in argon for stainless steel

Metal vapour emanating from the weld pool during tungsten-inert-gas (TIG) welding affects the arc welding process. To understand the transport mechanisms of metal vapour in a TIG arc, an axisymmetric computational model is developed that includes the tungsten cathode, stainless-steel anode workpiece and the arc plasma region self-consistently. The combined diffusion coefficient method, which calculates diffusion coefficients due to mole fraction gradients (ordinary diffusion), temperature gradients, pressure gradients and the electric field is used to treat iron–chromium–argon and iron–chromium–helium plasmas. It was found that in both cases, metal vapours can reach the cathode region. The effect of different diffusion coefficients on metal vapour transport was investigated. It was found that ordinary diffusion is the main driving force for upward metal vapour diffusion away from the anode workpiece in an argon arc. The diffusive transport carries the metal vapour into the recirculating convective flow, which then transports the metal vapour to the cathode region. Here the upward diffusion driven by the temperature gradient and electric field leads to the build of high concentrations of the metal vapours adjacent to the cathode. In the helium arc, in contrast, metal vapour is transported upwards from the workpiece by electric field diffusion, which is much stronger in this case. Spectroscopic measurements of atomic chromium emission show that metal vapour can reach the cathode region in an argon TIG arc, providing support for the predictions of the model. Only by taking into account all diffusion driving forces is it possible to predict the distribution of metal vapour in a TIG welding arc.     

Continuum modeling of size effects on the composition and stresses in nanoparticles of ionic solids with application to ceria

Owing to its broad potential applications, nanostructured ceria has been subject of intense investigation in the past few decades. Experiments have demonstrated that various material properties of the nanostructured ionic solids including ceria vary with the feature size. Here, we present a theoretical study of the size effects on the composition, defect concentrations and stresses in free-standing nanoparticles of nonstoichiometric ionic solids. To this end, a continuum model is developed which accounts for the highly nonlinear coupling between mechanical, chemical and electrical driving forces, and their effects on the thermodynamic equilibrium of the defect species. It is demonstrated that the model, once applied to the case of ceria, predicts size-dependent defect concentrations and surface stresses. It is further shown that the theoretical predictions of the size effects on the composition and lattice parameter are in good agreement with the experimental observations.     

Dust modelling using a combined CFD and discrete element formulation

The production and dispersal of airborne dust is an important issue in both environmental and industrial contexts. Dust pollution is a major environmental concern, and long exposure in occupational settings has been linked with numerous respiratory health issues. Industrial dust pollution can also present a significant explosion hazard, even in facilities with dust extraction systems. Computational models for dust generation and dispersal have, however, generally been formulated for specific geophysical applications and restricted to static, two‐dimensional, approaches. Here, we present a method for simulating dust production from a dynamic granular bed by using a three‐dimensional coupled discrete element method and Navier–Stokes computational model. Dust production is based on an energy formulation in which micro‐scale dust particles are assumed to overcome cohesion to macro‐scale grains. This model is used over the entire range of energies present within the system, from macro‐scale collisions to aerodynamic entrainment and bombardment of micro‐scale particles. The dust concentration is modelled as a scalar density field, which is advected and diffused through turbulence in the gas flow field. The model is tested against empirical predictions for two test cases, a slug of granular material dropped from a set height and air flow over a granular stockpile. Both give good agreement to the empirical relations, showing that the model can accurately predict the production and subsequent dispersal of dust from a dynamic granular bed. Copyright © 2012 John Wiley & Sons, Ltd.     

A General Method for the Rapid High Yield Preparation of Pure Arsonium Salts. Preparation Of (3-Alkoxy-Carbonyl-2-Oxopropyl)Triphenylarsonium Bromides

An easy, rapid method for the preparation of arsonium salts of high yield and purity, by heating an alkyl halide and triphenylarsine as a melt at about 80°C, is described.     

SOLVENT-FREE CONVERSION OF OXIRANES TO THIIRANES WITH THIOUREA

A simple and efficient method for the conversion of various oxiranes to the corresponding thiiranes using thiourea under solvent free conditions is described.     

A continuous-flow synthesis of annulated and polysubstituted furans from the reaction of ketones and α-haloketones

A synthesis of di-, tri- and tetra-substituted furans from reaction of the corresponding ketones and α-haloketones with LiHMDS is reported. Reaction under continuous-flow conditions gave increased yields and removed the need for external cooling when compared to the unoptimised batch conditions.     

Synthesis, structures and membrane properties of siloxane-imide co-polymers produced by aqueous polymerization

We report for the first time, the synthesis of siloxane-imide co-polymers by the reaction of mixtures of 1,4-bis(aminobutyl)tetramethyldisiloxane (ABTMDS) and 1,3-bis(4-aminophenoxy)benzene (TPE-R) with bisphenol A diphthalic anhydride (BPADA) using water as the polymerization solvent. A series of co-polymers were prepared incorporating 10, 20, 40 and 100 mol% of ABTMDS with the aromatic diamine TPE-R as the co-monomer. The synthesized co-polymers showed number average molecular weights in the range of 25,000–60,000. As expected the glass transition temperatures (T_gs) and moduli of the polymers were found to decrease with increasing amounts of the siloxane monomer and the homo-polymer containing only the siloxane diamine showing the lowest T_g (60 °C). The resulting polymers could be solution cast into strong and flexible membranes which showed significant decreases in water absorption and moisture permeability compared to the control polymer without siloxane groups. The polymers were characterized by FTIR, ¹³C and ¹H NMR, GPC, DSC and mechanical properties and structural comparisons were made with similar polymers made by standard solvent synthesis methods. Also cross-linked polymers were prepared by the reaction of ABTMDS with the aromatic homo-polymer control and their membrane properties were compared to those of the water synthesized siloxane co-polymers with a similar siloxane content.