Rearrangement of α-pinene oxide using a surface catalysed spinning disc reactor (SDR)

Isomerisation of α-pinene oxide to campholenic aldehyde was performed by immobilising zinc triflate based catalysts on the surface of a spinning disc reactor (SDR). Two types of catalyst have been studied and the influence of operating parameters such as rotational speed, feed flow rate and reaction temperature on conversion and selectivity towards campholenic aldehyde has been investigated in considerable detail. The findings of the study suggest that immobilising the catalyst on the reactor surface and performing the reaction in continuous mode has potential for achieving benefits of Green Chemical Technology (GCT).

Learning from mother nature:exploiting a biological antioxidant for the melt stabilisation of polymers

An overview of the antioxidant role of the biologically active form of vitamin E, α-tocopherol, in polyolefins is discussed. The effect of the vitamin antioxidant on the melt and colour stability of polyethylene (PE) and polypropylene (PP) is highlighted. It is shown that tocopherol is a highly effective antioxidant that results in superior melt stabilisation of polyolefins particularly when used at much lower concentration than that needed for conventional synthetic hindered phenol processing stabilisers. As with other hindered phenols,α-tocopherol imparts also some colour to the polymer but this is shown to be reduced drastically in the presence of other antioxidants, such as phosphites, or other additives, such as polyhydric alcohols.

Reactive processing of polymers:melt grafting of glycidyl methacrylate on ethylene propylene copolymer in the presence of a coagent

Glycidyl methacrylate (GMA) was grafted on ethylene-propylene copolymer during melt processing with peroxide initiation in the presence and absence of a more reactive comonomer (coagent), trimethylolpropane triacrylate (Tris). The characteristics of the grafting systems in terms of the grafting reaction yield and the nature and extent of the competing side reactions were examined. The homopolymers of GMA (Poly-GMA) and Tris (Poly-Tris) and the GMA-Tris copolymer (GMA-co-Tris) were synthesized and characterized. In the absence of the coagent, high levels of poly-GMA, which constituted the major competing reaction, was formed, giving rise to low GMA grafting levels. Further, this grafting system resulted in a high extent of gel formation and polymer crosslinking due to the high levels of peroxide needed to achieve optimum GMA grafting and a consequent large drop in the melt index (increased viscosity) of the polymer. In the presence of the coagent, however, the grafting system required much lower peroxide concentration, by almost an order of magnitude, to achieve the optimum grafting yield. The coagent-containing GMA-grafting system has also resulted in a drastic reduction in the extent of all competing reactions, and in particular, the GMA homopolymerization, leading to improved GMA grafting efficiency with no detectable gel or crosslinking. The mechanisms of the grafting reactions, in the presence and absence of Tris, are proposed.

Melt inclusions from volcan de Colima, Mexico: complex examples of magmatic differentiation

Melt inclusions are minute magma bodies trapped within growing crystals. Their chemical compositions are useful in deciphering pre-eruptive conditions and magma evolution. The present study examined melt inclusions trapped in phenocrysts from the 3rd and 4th magmatic cycles (1869-1988) at Volcan de Colima, Mexico. Melt inclusions have highly evolved chemical compositions: 65-77% SiO2, >12% A12O3, 3-6% Na2O and K20 and less than 5.5% Fe and Mg. Major element compositions suggest that they are strongly differentiated magmas controlled by fractionation of plagioclase, opx, cpx and hornblende. Water concentrations were measured to be 2.7-3.5 wt. % in cpx hosted inclusions and 0.3-0.7 wt % in opx and plagioclase. Trace element compositions are anomalously low and inversely correlate with water. From this we deduce that Colima lavas and scorias simultaneously differentiate and degas. Moreover, hornblende rim growth rates constrain the ascent of the Colima magmas to -100 days for passive eruptions and >4 days for plinian eruptions.

Ground-based electromagnetic (EM) and drill-hole ice and snow thickness and melt pond depth measurements during Polarstern cruise ARK-IX/4, ARK-XI/1, and ARK-XII

Drillhole-determined sea-ice thickness was compared with values derived remotely using a portable small-offset loop-loop steady state electromagnetic (EM) induction device during expeditions to Fram Strait and the Siberian Arctic, under typical winter and summer conditions. Simple empirical transformation equations are derived to convert measured apparent conductivity into ice thickness. Despite the extreme seasonal differences in sea-ice properties as revealed by ice core analysis, the transformation equations vary little for winter and summer. Thus, the EM induction technique operated on the ice surface in the horizontal dipole mode yields accurate results within 5 to 10% of the drillhole determined thickness over level ice in both seasons. The robustness of the induction method with respect to seasonal extremes is attributed to the low salinity of brine or meltwater filling the extensive pore space in summer. Thus, the average bulk ice conductivity for summer multiyear sea ice derived according to Archie's law amounts to 23 mS/m compared to 3 mS/m for winter conditions. These mean conductivities cause only minor differences in the EM response, as is shown by means of 1-D modeling. However, under summer conditions the range of ice conductivities is wider. Along with the widespread occurrence of surface melt ponds and freshwater lenses underneath the ice, this causes greater scatter in the apparent conductivity/ice thickness relation. This can result in higher deviations between EM-derived and drillhole determined thicknesses in summer than in winter.

Composition of melt inclusions and age of zircons of plagiogneisses from the Kola Superdeep Borehole

A comprehensive study of melt inclusions and SHRIMP dating of zircons from trondhjemite gneisses of the sequence VIII from the Kola Superdeep Borehole has revealed presence of old primary magmatic crystals with age up to 2887+/-15 Ma. This is not consistent with the previous view, according to which the oldest zircons from the Archean Complex in SG-3 are products of granulite metamorphism. Primary magmatic zircons of early generation (from 2887 to 2842 Ma) formed in deep-seated magma chambers during partial crystallization of CO2-saturated trondhjemite estimates on duration of generation of tonalite-trondhjemite-granite melts through partial melting of mafic rocks.

Melt climatology estimates for small to giant Antarctic icebergs, links to NetCDF files

We present four melt climatology estimates based on a simulation of Antarctic iceberg drift and melting that includes small, medium-sized, and giant tabular icebergs with a realistic size distribution. Drift and meltdown is simulated using vertical profiles of ocean currents, temperature, and salinity, which goes beyond the present standard in iceberg modeling. The climatology estimates based on simulations of small (SMA), 'small-to-medium'-sized (MED12 & MED123), and small-to-giant icebergs (ALL) exhibit differential characteristics: successive inclusion of larger icebergs leads to a reduced seasonality of iceberg melt and a shift of the mass input to the area north of 58°S, while less melt water is released into the coastal areas. This highlights the necessity to account for larger and giant icebergs in order to obtain accurate melt climatologies. The four monthly melt climatologies [mm/day] are available as netCDF files with 1°x1° spatial resolution and can be used, e.g., for sensitivity studies with uncoupled sea ice-ocean models, or as spatio-temporal templates for the redistribution of land ice from the Antarctic ice sheet over the Southern Ocean in climate models.

Mechanochemical Synthesis of Pharmaceutical Cocrystal Suspensions via Hot Melt Extrusion: Feasibility Studies and Physicochemical Characterisation

Engineered cocrystals offer an alternative solid drug form with tailored physicochemical properties. Interestingly, although cocrystals provide many new possibilities, they also present new challenges, particularly in regard to their design and large-scale manufacture. Current literature has primarily focused on the preparation and characterization of novel cocrystals typically containing only the drug and coformer, leaving the subsequent formulation less explored. In this paper we propose, for the first time, the use of hot melt extrusion for the mechanochemical synthesis of pharmaceutical cocrystals in the presence of a meltable binder. In this approach, we examine excipients that are amenable to hot melt extrusion, forming a suspension of cocrystal particulates embedded in a pharmaceutical matrix. Using ibuprofen and isonicotinamide as a model cocrystal reagent pair, formulations extruded with a small molecular matrix carrier (xylitol) were examined to be intimate mixtures wherein the newly formed cocrystal particulates were physically suspended in a matrix. With respect to formulations extruded using polymeric carriers (Soluplus and Eudragit EPO, respectively), however, there was no evidence within PXRD patterns of either crystalline ibuprofen or the cocrystal. Importantly, it was established in this study that an appropriate carrier for a cocrystal reagent pair during HME processing should satisfy certain criteria including limited interaction with parent reagents and cocrystal product, processing temperature sufficiently lower than the onset of cocrystal Tm, low melt viscosity, and rapid solidification upon cooling.

Initiation of Orderly Spinning Detonation Waves via Phased Sparking

Thesis (Master's)--University of Washington, 2016-06