Martin Roe

The electron microscope appearance of the subchondral bone plate in the human femoral head in osteoarthritis and osteoporosis

The subchondral bone plate supports the articular cartilage in diarthrodial joints. It has a significant mechanical function in transmitting loads from the cartilage into the underlying cancellous bone and has been implicated in the destruction of cartilage in osteoarthritis (OA) and its sparing in osteoporosis (OP), but little is known of its composition, structure or material properties. This study investigated the microscopic appearance and mineral composition of the subchondral bone plate in femoral heads from patients with OA or OP to determine how these correspond to changes in composition and stiffness found in other studies. Freeze‐fractured full‐depth samples of the subchondral bone plate from the femoral heads of patients with osteoarthritis, osteoporosis or a matched control group were examined using back scattered and secondary emission scanning electron microscopy. Other samples were embedded and polished and examined using back‐scattered electron microscopy and electron probe microanalysis. The appearances of the samples from the normal and osteoporotic patients were very similar, with the subchondral bone plate overlayed by a layer of calcified cartilage. Osteoporotic samples presented a more uniform fracture surface and the relative thicknesses of the layers appeared to be different. In contrast, the OA bone plate appeared to be porous and have a much more textured surface. There were occasional sites of microtrabecular bone formation between the trabeculae of the underlying cancellous bone, which were not seen in the other groups, and more numerous osteoclast resorption pits. The calcified cartilage layer was almost absent and the bone plate was apparently thickened. The appearance of the osteoarthritic subchondral bone plate was, therefore, considerably different from both the normal and the osteoporotic, strongly indicative of abnormal cellular activity.

Role of quantitative mineralogical analysis in the investigation of sites contaminated by chromite ore processing residue

A range of techniques, normally associated with mineralogical studies of soils and sediments, has been used to characterise the solid materials found on sites contaminated with chromite ore processing residue (COPR). The results show that a wide range of minerals are present, many of which are found extensively in high-temperature synthetic systems such as cements and clinkers and their low temperature hydration products. Thus, the minerals in COPR can be divided into three main categories: unreacted feedstock ore (chromite); high temperature phases produced during chromium extraction (brownmillerite, periclase and larnite); and finally, minerals formed under ambient weathering conditions on the disposal sites (brucite, calcite, aragonite, ettringite, hydrocalumite, hydrogarnet). Apart from chromite, chromium occurs in brownmillerite, ettringite, hydrocalumite and hydrogarnet. Detailed study of the chemistry and stoichiometry of chromium-bearing phases in conjunction with phase abundance provides a quantitative description of the solid state speciation of Cr(III) and Cr(VI) in and amongst these minerals and in the COPR as a whole. Of the total chromium present in the samples most, approximately 60-70% is present as Cr(III) in chromite, whilst brownmillerite also represents a significant reservoir of Cr(III) which is approximately 15% of the total. The remaining chromium, between 20 and 25%, is present as Cr(VI) and resides mainly in hydrogarnet, and to a slightly lesser extent in hydrocalumite. In the latter, it is present principally in an exchangeable anionic form. Chromium (VI) is also present in ettringite, but quantitatively ettringite is a much less important reservoir of Cr(VI), accounting for approximately 3% of total chromium in one sample, but less than 1% in the other two. This description provides insight into the processes likely to control the retention and release of Cr(VI) from COPR-contaminated sites. Such information is of particular value in chemical modelling of the system, in risk assessment and in the development of methods of informed remediation.

The influence of mineralogy on weathering rates and processes in an acid-sensitive granitic catchment

Abstract Weathering in an upland catchment on granitic parent material has been studied by chemical and mineralogical analyses of soils. Long-term weathering rates for base cations, calculated from chemical analyses of the mineral horizons from soil profiles using Zr as an internal, immobile, index element, are among the smallest recorded for Scottish soils (1.7–3.1 meq m−2 a−1), indicating that these soils are susceptible to acid deposition. Sodium is the base cation lost to the greatest extent from the soils, due to weathering of plagioclase feldspar, mainly in the coarse size-fractions. Calcium is lost not only from plagioclase feldspar, but also from hornblende, grains of which show dissolution etch pits and denticulate surface features when examined by scanning electron microscopy. Weathering of hornblende, present in basic inclusions in the granite, is a significant weathering process in these soils. A range of values for 87Sr/86Sr ratios in stream-waters confirms the spatial variability of the material supplying Ca to the streams. The current weathering rate, calculated from input–output budgets to be 28.9 meq m−2 a−1, is much greater than the long-term weathering rate, but small compared to other catchments on similar parent material.

Enhanced conductivity of reduced graphene oxide decorated with aluminium oxide nanoparticles by oxygen annealing

A process involving the filtration of graphene oxide (GO) dispersion through an alumina membrane, followed by oxygen annealing to synthesize alumina nanoparticles exclusively at the edges of holes or vacancies in the reduced graphene oxide (rGO) plane, is used to prepare paper-like composites with a 21% enhanced electrical conductivity. Moreover, the rGO/alumina nanocomposites have a smaller band gap and hydrophilic properties.

Effects of KOH etching on the properties of Ga-polar n-GaN surfaces

The effects of a KOH treatment on the properties of n-type GaN surfaces and associated Au/n-GaN contacts have been investigated by X-ray photoelectron spectroscopy, atomic force microscopy, reflection high-energy-electron diffraction, current–voltage and electron-beam-induced current characterization. Ga-polar surfaces grown by molecular beam epitaxy and metal–organic chemical vapour deposition were compared. A decrease in electron barrier height and an increase in non-radiative recombination properties of Au/n-GaN contacts were found with KOH treatment, correlated with an increase of surface Ga vacancies, an increase in surface N–H2 content and a decrease in surface C contamination. A 0.3-eV shift in the Ga3d peak position towards the valence band and a reduction in the dislocation contrast were observed for the case of molecular-beam-epitaxy-grown GaN only, demonstrating that surface Ga vacancies and threading dislocations play only a limited role in defining the resultant metal/GaN contact properties. Accordingly, the surface atomic content and the resulting surface states, following KOH treatment, should be taken into consideration when appraising the electrical properties of n-GaN surfaces and the performance of associated metallic contacts.

Peptide-directed crystal growth modification in the formation of ZnO

Biomolecule-mediated synthesis is fascinating in terms of the level of control and the intricate hierarchical structures of the materials that can be produced. In this study we compare the behavior of a phage display identified peptide, EAHVMHKVAPRP (EM-12) with that of a mutant peptide EAHVCHKVAPRP (EC-12), having additional complexation capability, on the formation of ZnO from solution. The synthesis conditions (Zn(CH3COO)2-NH3 hydrothermal method at 50 °C) were chosen to generate rod-shaped ZnO via layered basic zinc salts (LBZs) as intermediates. Both peptides affected the crystal formation process by moderating the amount of Zn2+ ions in solution (EC12 having a greater effect than EM12) but only EC12 was shown to interact with the solid phase(s) formed during the reaction. Depending on the peptide concentration used, EM-12 was shown to delay and/or suppress ZnO formation. In contrast, additions of EC-12, although leading to the retention of higher levels of Zn2+ ions in solution did not similarly delay the transformation of the intermediate phases to ZnO but were found to dramatically modify the morphology of ZnO crystallites with mushroom shaped crystals being formed. From the results of detailed materials characterization and changes in the morphology observed, the interactions between the peptide(s) and solution and solid state species present during the process of ZnO crystal formation in the presence of EM-12 and EC-12 are proposed.

Use of hydrofluoric acid dissolution for the concentration of dickite and nacrite from kaolin deposits: an FTIR study

Abstract A series of kaolin-rich mineral samples was treated with hydrofluoric acid (HF) and the residual material characterized using infrared (IR) spectroscopy, supplemented by scanning electron microscope (SEM) observations. By examining the hydroxyl-stretching region of the IR spectra before and after treatment with hydrofluoric acid, it was possible to identify the three kaolin polytypes - kaolinite, dickite and nacrite with greater certainty. The SEM observations suggested that the rate of dissolution of the kaolin phase was largely dependent on particle size. In general, dickite and nacrite tend to occur in the coarser clay fractions, and for this reason the finer-grained kaolinite is preferentially dissolved by the HF treatment. However, in the Keokuk kaolinite, which occurs in exceptionally large particles, it was still possible to concentrate a dickitic fraction by HF treatment, suggesting that in some cases kaolinite may be more susceptible to HF dissolution for reasons other than particle size. The IR spectra of disordered kaolinite could be interpreted as arising from a mixture of kaolinite and dickite components. However, both components dissolve at the same rate in HF, supporting the idea that disordered kaolinite consists of an intimate association of randomly stacked dickite-like and kaolinite-like components.

Characterisation of archaeological glass mosaics by electron microscopy and X-ray microanalysis

The combined techniques of scanning electron microscopy, energy dispersive X-ray analysis, transmission electron microscopy (TEM) and selected area electron diffraction are used to characterise the microstructures of opaque coloured glass mosaics from a mediaeval church in Torcello, Italy. Comparison of MgO/K2O ratios allows distinction between mediaeval and modern glass artefacts to be made. TEM investigation of inclusions indicates that relict silica is responsible for the speckled appearance of an impure mediaeval glass artefact, whilst a fine scale dispersion of elemental Cu nanoparticles is considered responsible for the orange-red colouration of a modern glass artefact.