Quantitative X-ray powder diffraction analysis of clay minerals in Australian coals using Rietveld methods

The mineralogy of clay-rich mineral matter isolated from a range of Australian bituminous coals has been evaluated in quantitative terms from X-ray powder diffraction (XRD) patterns using a Rietveld-based data processing technique. The chemical composition of coal ash derived from this mineral matter has been calculated and compared to the directly determined composition of the ash prepared from the same coal samples. Although there are some minor differences due in part to uncertainty regarding the actual composition of several minerals, the compositions indicated by the two methods show a relatively high correlation, suggesting that the Rietveld technique provides mineralogical analyses that are consistent with independently determined chemical data. Comparison of the normalised clay mineral percentages from the Rietveld analysis to quantitative interpretations based on a peak intensities in glycolated and heat-treated oriented aggregates of the respective clay fractions also shows a high correlation, confirming mutual consistency of the two different mineralogical analysis methods. Such quantitative mineralogical data are significant to a range of coal exploration, mining and utilization activities, including seam correlation, material handling and ash and slag formation in combustion processes.     

The hot compaction behaviour of woven oriented polypropylene fibres and tapes. I. Mechanical properties

The aim of this work was to establish the important parameters that control the hot compaction behaviour of woven oriented polypropylene. Five commercial woven cloths, based on four different polypropylene polymers, were selected so that the perceived important variables could be studied. These include the mechanical properties of the original oriented tapes or fibres, the geometry of the oriented reinforcement (fibres or tapes), the mechanical properties of the base polymer (which are crucially dependant on the molecular weight and morphology), and the weave style. The five cloths were chosen so as to explore the boundaries of these various parameters, i.e. low and high molecular weight: circular or rectangular reinforcement (fibres or tapes): low or high tape initial orientation: coarse or fine weave.A vital aspect of this study was the realisation that hot compacted polypropylene could be envisaged as a composite, comprising an oriented ‘reinforcement’ bound together by a matrix phase, formed by melting and recrystallisation of the original oriented material. We have established the crucial importance of the properties of the melted and recrystallised matrix phase, especially the level of ductility, in controlling the properties of the hot compacted composite.     

A Maternal High Fat Diet Has Long‐Lasting Effects on Skeletal Muscle Lipid and PLIN Protein Content in Rat Offspring at Young Adulthood

A maternal high fat diet (HFD) can have adverse effects on skeletal muscle development. Skeletal muscle PLIN proteins (PLIN2, 3 and 5) are thought to play critical roles in lipid metabolism, however effects of HFD on PLIN and lipases (HSL, ATGL, CGI‐58) in mothers as well as their offspring have yet to be investigated. The primary objective of this study was to determine whether maternal HFD would influence skeletal muscle lipase and PLIN protein content in offspring at weaning (19d) and young adulthood (3mo). Female rats (28d old, n = 9/group) were fed control (CON, AIN93G, 7 % soybean oil) or HFD (AIN93G, 20 % lard) for 10 weeks prior to mating and throughout pregnancy and lactation. All offspring were weaned to CON [n = 18/group, 1 female and 1 male pup per litter were studied at weaning (19d) and 3mo of age]. There was no effect of sex for the main outcomes measured in plantaris, therefore male and female data was combined. Maternal HFD resulted in higher triacylglycerol content in pups at 3mo (p < 0.05), as well as in the dams (p = 0.015). Maternal HFD resulted in higher PLIN5 content in pups at weaning and 3mo (p = 0.05). PLIN2 and PLIN5 content decreased at 3mo versus weaning (p < 0.001). HFD dams had a higher PLIN3 content (p = 0.016). Diet had no effect on ATGL, CGI‐58, or HSL content. In conclusion, exposure to a maternal HFD resulted in higher skeletal muscle lipid and PLIN5 content in plantaris of offspring through to young adulthood.     

Fiber Strength After Grain Growth in Nextel™ 610 Alumina Fiber

Nextel^? 610 alumina fiber tows were heat‐treated at 1100°C–1500°C for 1 to 100 h in air. Tensile strengths and Weibull moduli were measured for 30 filaments after each heat‐treatment. 3‐D grain size and orientation distributions were described using oblate ellipsoids. The number of grains in a 1 inch gauge length and grains with the largest major and minor ellipsoid‐axes were determined from these distributions. The grain with the largest K_EFF for mixed‐mode fracture was also determined, using the maximum energy release rate criteria from grain‐size and orientation distributions. Grain‐size dependence of tensile strength and Weibull modulus was evaluated. Strength had no obvious dependence on grain size for fibers with average major‐axes smaller than 0.25 μm. For fibers with larger grains, grain‐size dependence may involve flaws originating from clumps of grains, rather than a single grain. Possible relationships between strength and grain‐size and other causes of strength degradation after heat‐treatment are discussed.     

Kinetics and thermodynamics of sulfuric acid-mediated cleavage of substituted diaryl sulfones

The cleavage of di-p-tolyl sulfone with concentrated sulfuric acid has been shown to occur at elevated temperatures (>120°C). The products were confirmed as the corresponding sulfonic acids by gas chromatography-mass spectrometry analysis of the sulfonate ester derivatives. The cleavage reactions of a series of di-p-substituted diaryl sulfones with sulfuric acid have been studied. A method using a double end-point titration has been used to quantify the amounts of sulfonic acid formed as the reactions proceed. These data have been used to construct second-order rate plots over a range of temperatures and to determine rate constants for the cleavage reactions. The second-order rate plots showed good linearity. Activation energies were determined from Arrhenius plots of the second-order rate constants over a range of temperatures. The presence of electron-donating groups decreases the activation energy of the reaction, whereas the presence of electron-with-drawing groups increases the activation energy of the reaction.     

Relationship Between Structure and Coordination Strength of N and N,O-Hybrid Donor Ligands with Trivalent Lanthanides

ABSTRACT

To effectively separate lanthanides (Ln(III)) from actinides (An(III)), symmetrical 2,2′-bipyridyl (Bpy), 1,10-phenanthroline (Phen), and unsymmetrical N-methyl-N-tolyl-1,10-phenanthroline-2-carboxamide (MeTol-PTA) were investigated. According to the crystal structures and EXAFS experiments, the decreasing ionic radius from light to heavy Ln led to decreases in the Ln–N (Bpy) and Ln–N (Phen) distances, while log β simply increased due to the electrostatic interaction and the order of Ln–O (MeTol-PTA) < Ln–N (Bpy, Phen) < Ln–N (MeTol-PTA) was obtained. This indicated that the bulky phenanthroline moiety of MeTol-PTA may not allow N (MeTol-PTA) to come close to Ln. Consequently, the log β of MeTol-PTA exhibited a local maximum (around Nd).     

Synthesis and Evaluation of Water‐Soluble Prodrugs of Ursodeoxycholic Acid (UDCA), an Anti‐apoptotic Bile Acid

Ursodeoxycholic acid (UDCA) is a bile acid with demonstrated anti‐apoptotic activity in both in vitro and in vivo models. However, its utility is hampered by limited aqueous solubility. As such, water‐soluble prodrugs of UDCA could have an advantage over the parent bile acid in indications where intravenous administration might be preferable, such as decreasing damage from stroke or acute kidney injury. Five phosphate prodrugs were synthesized, including one incorporating a novel phosphoryloxymethyl carboxylate (POMC) moiety. These prodrugs were highly water‐soluble, but showed significant differences in chemical stability, with oxymethylphosphate prodrugs being the most unstable. In a series of NMR experiments, the POMC prodrug was bioactivated to UDCA by alkaline phosphatase (AP) faster than a prodrug containing a phosphate directly attached to the alcohol at the 3‐position of UDCA. Both of these prodrugs showed significant anti‐apoptotic activity in a series of in vitro assays, although the POMC prodrug required the addition of AP for activity, while the other compound was active without exogenous AP.     

Optimizing the performance of aerosol photoacoustic cells using a finite element model. Part 2: Application to a two-resonator cell

Abstract

Photoacoustic spectroscopy (PAS) measures aerosol absorption in a noncontact manner, providing accurate absorption measurements that are needed to improve aerosol optical property representations in climate models. Central to PAS is resonant amplification of the acoustic pressure wave generated from laser-heated aerosol transferring heat to surrounding gas by a photoacoustic cell. Although this cell amplifies pressure sources from aerosol absorption (signal), it also amplifies noise and background sources. It is important to maximize the cell signal-to-background ratio (SBR) for sensitive absorption measurements. Many researchers have adopted the two-resonator cell design described by Lack et al. (2006 Lack, D. A., E. R. Lovejoy, T. Baynard, A. Pettersson, and A. R. Ravishankara. 2006. Aerosol absorption measurement using photoacoustic spectroscopy: Sensitivity, calibration, and uncertainty developments. Aerosol Sci. Technol. 40 (9):697–708. doi: 10.1080/02786820600803917.[Taylor &; Francis Online], [Web of Science ®] , [Google Scholar]). We show that the uncertainty in PAS measurements of aerosol absorption using this two-resonator cell is significantly degraded by its large sensitivity to background contributions from laser scattering and absorption at the cell windows. In Part 1, we described the use of a finite element method (FEM) to predict cell acoustic properties, validated this framework by comparing model predictions to measurements, and used FEM to test various strategies applied commonly to single-resonator cell optimization. In this second part, we apply FEM to understand the excitation of resonant modes of the two-resonator cell, with comparison measurements demonstrating accurate predictions of acoustic response. We perform geometry optimization studies to maximize the SBR and demonstrate that the laser–window interaction background is reduced to undetectable levels for an optimal cell. This optimized two-resonator cell will improve the sensitivity and accuracy of future aerosol absorption measurements.     

The best objective function for seeded batch crystallization

Although many researchers have optimized the operation of seeded batch crystallization, there remains little understanding of the effect of the choice of objective function on the optimization and no consensus on which objective function is best. In this work, different objective functions for seeded batch crystallization are compared by calculating the supersaturation trajectory that minimizes each objective function and then comparing the results of each trajectory. We show that some objective functions lead to trajectories that cause excessive nucleated mass and should be avoided. We conclude that the best objective function in most cases is to minimize the nucleated mass. This also corresponds to maximizing the growth of seeds, and leads to a product with a large volume mean size. We also show that the width of the product crystal size distribution can be controlled much more effectively by manipulating seed properties than by adjusting the supersaturation trajectory. © 2012 American Institute of Chemical Engineers AIChE J, 59: 390–398, 2013     

Brittle‐ductile transitions in polyethylene

The failure mode of a number of polyethylenes has been studied under predominantly plane strain conditions. Square section samples, notched on all sides, have been tested in tension to failure over a range of crosshead speeds and temperatures. Integration under the subsequent load displacement curve has allowed the total energy, energy to peak load, and energy after peak load to be determined. The data have been analyzed in terms of the ratio of the energy after the peak load to the total energy. The results show that the material can change from brittle to ductile failure as a function of test speed. At a suitable temperature we have observed brittle‐like failure at the highest and lowest test speeds and ductile failure at intermediate speeds. The resulting failure surface features correlate very strongly with the energy ratio analysis—flat smooth surfaces where low energy ratios are seen and large ductile tearing where high ratios are seen. The effect of molecular weight and polydispersity will be shown and possible failure mechanisms discussed.