Hyperbranched Polymers Containing Cyclopentadienyliron Complexes

A number of hyperbranched polymers containing cyclopentadienyliron moieties were prepared using the A₂+B₃ method. The A₂ compounds used were common diols, dithiols or dichloroarenecomplexes. B₃ compounds included either prepared star-shaped molecules or a purchased triol. The effect of the reaction conditions on the properties of the products was probed. Analysis of the prepared polymers was conducted using ¹H and ¹³C NMR, viscometry, differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Viscometry values were generally found to be low, in the range of 0.175–0.300 dl/g. TGA showed losses starting at approximately 230°C and ending at 280°C, corresponding to the decomposition of the cyclopentadienyliron moiety. Degradation of the polyether backbone was found to occur starting at 390–567°C. Glass transition temperatures were found to be between 60 and 134°C, whereas melting temperatures ranged from 155 to 190°C.     

Direct methanol alkaline fuel cells with catalysed anion exchange membrane electrodes

Membrane electrodes prepared by chemical deposition of platinum directly onto the anion exchange membrane electrolyte were tested in direct methanol alkaline fuel cells. Data on the cell voltage against current density performance and anode potentials are reported. The relatively low fuel cell performance was probably due to the low active surface area of Pt deposits on the membrane comparing to other membrane electrode assembly (MEA) fabrication methods. However, the catalysed membrane electrode showed good performance for oxygen reduction. A reduction in cell internal resistance was also obtained for the catalysed membrane electrode. By combining the catalysed membrane electrodes with a catalysed mesh, maximum current density of 98 mA cm^–2 and peak power density of 18 mW cm^–2 were achieved.     

Abrasive wear in filled elastomers

The abrasive wear of rubbers is strongly affected by the filler particles dispersed in the elastomer matrix. The fillers are incorporated usually for the purposes of mechanical reinforcement and improving the conductivity of the neat resins. It is found that the wear rates of the filled silicone rubbers increase slowly with filler concentration until a critical volume fraction,v _c, is reached, at which point they increase very rapidly with increasing filler concentration. This behaviour appeared to be universal in all the filled silicones we studied, regardless of the type of filler and silicone rubber used. However the magnitude of the critical filler fraction,v _c, can be changed significantly with the filler shape, resin cross-linking density and filler surface treatments. No reasonable relationship could be found between this wear behaviour and the mechanical properties measured in a macroscopic manner. Experimental evidence suggests that the incipient cracks that lead to wear losses may start within the thin layers of highly stressed material, the damage zones, surrounding the rigid particles. A simple model taking into account the stress concentration induced by the rigid fillers shows excellent correlation between the wear rate and the damage zones volume. With this new model, the observed wear behaviours can be explained satisfactorily.     

Microstructural studies of aluminium-silicon alloy reinforced with alumina fibres

The microstructure of an alumina fibre reinforced Al-7wt% Si alloy has been investigated. It was shown that the Al-Si eutectic structure which characterized this alloy was markedly changed by the presence of the fibres, with coarsening of silicon particles and a reduction in primary aluminium grain size. The coarse silicon particles exhibited twinning but no orientation relationship with the aluminium. Fine silicon precipitates were also present and these had a cube-cube orientation relationship with the aluminium lattice. Lath-like intermetallics, FeSiAl₅ and FeSi₂Al₄ with monoclinic and tetragonal structures, were identified which existed in equilibrium and had the epitaxial relationship (001)_mono//(001)_tet and [100]_mono//[100]_tet. The iron was a contaminant introduced in the course of composite fabrication.Dislocations were a common feature of the aluminium matrix, with a typical density of 4×10⁷mm^–2. Nevertheless, dislocation hardening of the metal matrix was not detected. No evidence of Mg₂Si precipitates in the metal matrix was found, but the small addition (0.2wt%) of magnesium to the alloy was discovered to segregate at the fibre-aluminium interface. This segregation was believed to result in improved wettability of the two constituents, encouraging the formation of a strong fibre-matrix bond, and producing desirable properties of the composite in the transverse direction.     

Characterization of polyethylene/EPDM/silicon dioxide multicomponent composites by solid-state dynamic mechanical spectroscopy

Various composites of polyethylene, ethylene propylene diene rubber (EPDM), and filler are milled and analysed by solid-state dynamic mechanical spectroscopy. The filler used is silicon powder with an oxidized surface. This filler is a model for materials with siliceous surfaces. The torsion pendulum measurements show that the multicomponent composites exhibited complex viscoelastic behaviour. For composites of polyethylene and silicon dioxide, there is evidence of particle-particle interactions. In composites which include polyethylene, rubber and filler, interactions of the polyethylene and especially of the rubber with the filler surface are significant. Treatment of the filler surface with gamma-aminopropyltriethoxysilane (-APS) or gamma-methacryloxypropyltrimethoxysilane (-MPS) has a significant influence on the resultant composite dynamic mechanical spectrum. Maleic anhydride grafting of the EPDM rubber also changes the character of the composites. These composites appear to exhibit complex morphologies, which may be controlled to a certain extent by filler surface treatment and grafting to the rubber. There is evidence for a chemical reaction between the maleic anhydride modification of the EPDM and -APS during processing on the roll mill. Prediction of the composite properties using the extended van der Poel model is qualitatively useful.     

Microstructure property relationship in Pyrex glass composites reinforced with Nicalon fibres

Detailed microstructural studies have been carried out on a series of composites consisting of Pyrex glass reinforced with Nicalon fibres. A variety of techniques has been employed, including X-ray and electron diffraction, electron-probe microanalysis and thin foil analytical electron microscopy. In parallel, mechanical tests have been performed on the composites and measurements have been made of the fibre-matrix bond.Substantial amounts of cristobalite have been identified in the matrix, up to 48% by volume in some cases. At such levels, microcracking is a common occurrence due to the high differential contraction between the matrix constituents upon cooling, which leads to matrix disintegration upon mechanical testing. A second microstructural feature which affects the mechanical behaviour of the composite concerns the fibre-matrix interface and, in particular, the chemistry of the outermost (200 nm) surface regions of the fibre. The amount of graphite here is shown to affect directly the strength of the fibre-matrix bond and, in turn, the degree of fibre pull out and the mechanical properties of the composite.     

An International Collaborative Study on Trypsin Inhibitor Assay for Legumes,Cereals, and Related Products

For determining trypsin inhibitor activity (TIA) in soy products, the American Oil Chemists' Society (AOCS) Method Ba 12-75 has been used. It measures differences in absorbance at 410 nm of bovine trypsin activity toward a synthetic substrate (Nα-benzoyl-DL-arginine-p-nitroanilide) in the absence and presence of an inhibitor. Recently, a significantly improved method was developed (JAOCS, 2019, 96:635–645), featuring 5 mL of total assay volume, enzyme-last sequence, and single inhibitor level in duplicate. It is proposed as the AOCS Method Ba 12a-2020. As a part of the AOCS method approval process, a collaborative study involving 12 international laboratories was conducted to evaluate the performance of the proposed method. The study involved measuring TIA in 10 selected test samples plus a blind duplicate. They included soybeans, pulses, cereals, and their processed products (flours, concentrates, and isolates). After rigorous statistical treatment of the data, only three outliers were removed from the data of two samples. Repeatability relative standard deviations (RSDr) for the 11 samples ranged from 0.99% to 5.52%. Reproducibility RSD (RSD_R) ranged from 7.07% to 22.92%, with seven samples having RSD_R around 10% or less. The remaining four samples had very low TIA, and their RSD_R values ranged from 13.34% to 22.92%. The study has demonstrated reliable performance of the proposed AOCS method. Several collaborators carried out additional experiments addressing some aspects of the method, leading to further refinements. The proposed method is undergoing evaluation by the AOCS Uniform Methods Committee for adoption as an Official Method for measuring TIA in various legume and grain products.     

The influence of composition and processing parameters on the mechanical properties and erosion response of Ni + TiB2 coatings

Sputtered Ni + TiB₂ coatings have been shown to protect Inconel* 718 and Ti-6A1-4V substrates from solid particle erosion. However, before new erosion-resistant coatings can be efficiently designed, it is essential that the role of mechanical properties in determining erosion resistance be fully understood. In this investigation, nanoindentation techniques were used to quantify the effects of substrate preparation, coating composition, and sputtering process parameters on the elastic moduli and indentation hardness of thin coatings deposited on Ti-6A1-4V and Inconel 718 substrates. The influence of these parameters on coating adhesion was determined using a conventional scratch test. Elastic moduli, indentation hardnesses, and coating adhesion were correlated with erosion behavior. The erosion resistance of those coatings that exhibited microscopic ductility is dependent on the nodule diameter and coating properties such as hardness, elastic modulus, and fracture toughness. Inconel 718 is a trademark of The International Nickel Co.     

Executive Perspectives on Top Risks for 2015

This article summarizes the results of Executive Perspectives on Top Risks for 2015, a study conducted by North Carolina State University’s ERM Initiative and Protiviti. For more information, visit www.protiviti.com/TopRisks.