Automatic mechanism generation for the combustion of advanced biofuels: A case study for diethyl ether

Advanced biofuels have the potential to supplant significant fractions of conventional liquid fossil fuels. However, the range of potential compounds could be wide depending on selected feedstocks and production processes. Not enough is known about the engine relevant behavior of many of these fuels, particularly when used within complex blends. Simulation tools may help to explore the combustion behavior of such blends but rely on robust chemical mechanisms providing accurate predictions of performance targets over large regions of thermochemical space. Tools such as automatic mechanism generation (AMG) may facilitate the generation of suitable mechanisms. Such tools have been commonly applied for the generation of mechanisms describing the oxidation of non-oxygenated, non-aromatic hydrocarbons, but the emergence of biofuels adds new challenges due to the presence of functional groups containing oxygen. This study investigates the capabilities of the AMG tool Reaction Mechanism Generator for such a task, using diethyl ether (DEE) as a case study. A methodology for the generation of advanced biofuel mechanisms is proposed and the resultant mechanism is evaluated against literature sourced experimental measurements for ignition delay times, jet-stirred reactor species concentrations, and flame speeds, over conditions covering φ = 0.5–2.0, P = 1–100 bar, and T = 298–1850 K. The results suggest that AMG tools are capable of rapidly producing accurate models for advanced biofuel components, although considerable upfront input was required. High-quality fuel specific reaction rates and thermochemistry for oxygenated species were required, as well as a seed mechanism, a thermochemistry library, and an expansion of the reaction family database to include training data for oxygenated compounds. The final DEE mechanism contains 146 species and 4392 reactions and in general, provides more accurate or comparable predictions when compared to literature sourced mechanisms across the investigated target data. The generation of combustion mechanisms for other potential advanced biofuel components could easily capitalize on these database updates reducing the need for future user interventions.     

Synthesis and lithographic applications of highly metallized cluster-based polyferrocenylsilanes

We report the use of a cobalt-clusterized polyferrocenylsilane (Co-PFS) as a precursor to patterned ferromagnetic ceramics. Co-PFS was synthesized. Functioning as a negative resist, Co-PFS lines with widths of 10-300 μm were patterned using UV-photolithography, while features as small as 500 nm were afforded by electron-beam lithography. Subsequent pyrolytic treatment of the lithographically patterned Co-PFS yielded ferromagnetic ceramics containing Fe/Co nanoparticles. Due to its high metal-loading, Co-PFS is a good etch resist for oxygen and hydrogen plasma reactive ion etching. Reactive ion etching of a thin film of Co-PFS in a secondary magnetic field allowed direct access to ferromagnetic ceramic films, providing a viable alternative to pyrolysis.     

ChemInform Abstract: Ligand Dependence of Metal—Metal Bonding in the d3d3 Dimers M2X9n- (MIII: Cr,Mo, W; MIV: Mn,Tc, Re; X: F,Cl, Br,I)

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.     

Safer Polyurethane Foams with Cyclic Carbonates

Polyurethanes (PUs) are a class of materials usually synthesized from isocyanates, diols, and water. Water is essential for producing carbon dioxide (CO₂) which is used for the self-blowing of the foams. Due to safety concerns with the production of isocyanates, alternative chemistries have been evaluated and cyclic carbonate systems have shown great promise. In a recent advancement by Bourguignon, Grignard, and Detrembleur, a cyclic carbonate and diamine system is capable of generating CO₂ for self-blowing through hydrolysis of the carbonate-based monomer. The authors demonstrate that with a simple variation of the diamine monomer a wide range of physical and thermo-mechanical properties were achievable. This work represents a significant step towards safer and more environmentally friendly PUs.     

The changing biochemical composition and organisation of the murine oocyte and early embryo as revealed by Raman spectroscopic mapping

Despite an exponential uptake in recent years of assisted reproductive techniques, such as in vitro fertilisation, much is still not fully understood about the biochemical modifications that take place during the development and maturation of the egg and embryo. As such, in order to improve the efficiency of these techniques, furthering our understanding of the processes that underpin oocyte and embryo development is necessary. Raman spectroscopic mapping as a technique enables the investigation of biochemical variation within intact cells without the need for labelling. Here, Raman maps of fixed immature and mature oocytes along with early stage embryos were collected using 785 nm excitation and a step size of 2 µm. The results were analysed using both univariate and multivariate techniques. It was found that significant macromolecular accumulation took place during oocyte maturation, while a decrease in total lipid content consistent with the formation of new cellular membranes is observed upon embryo cleavage. Furthermore, an observed asymmetrical localisation of macromolecules in the mature oocyte may indicate the existence of cytoplasmic polarisation, a phenomenon that has been observed in the eggs of lower organisms. As such, these results indicate that Raman spectroscopic mapping may present an alternative analytical tool for investigating the biochemistry of egg and embryo development. In particular, these results indicate that temporal Raman analysis may help to reveal the existence of cytoplasmic polarisation in the murine egg. Copyright © 2011 John Wiley & Sons, Ltd.