The first x-ray diffraction peak of water as a function of temperature in the range 4 – 63 °C

X-ray diffraction structure functions for water flowing in a 1.5 mm diameter siphon in the temperature range 4 – 63 °C were obtained using a 20 keV beam at the Australian Synchrotron. These functions were compared with structure functions obtained at the Advanced Light Source for a 0.5 mm thick sample of water in the temperature range 1 – 77 °C irradiated with an 11 keV beam. The two sets of structure functions are similar, but there are subtle differences in the shape and relative position of the two functions suggesting a possible differences between the structure of bulk and siphon water. In addition, the first structural peak (Q0) for water in a siphon, showed evidence of a step-wise increase in Q0 with increasing temperature rather than a smoothly varying increase. More experiments are required to investigate this apparent difference.

A neutron diffraction investigation of residual stresses in rail ends after severe deformation of rail surfaces

Insulated rail joints (IRJs) are a primary component of the rail track safety and signalling systems. Rails are supported by two fishplates which are fastened by bolts and nuts and, with the support of sleepers and track ballast, form an integrated assembly. IRJ failure can result from progressive defects, the propagation of which is influenced by residual stresses in the rail. Residual stresses change significantly during service due to the complex deformation and damage effects associated with wheel rolling, sliding and impact. IRJ failures can occur when metal flows over the insulated rail gap (typically 6-8 mm width), breaks the electrically isolated section of track and results in malfunction of the track signalling system. In this investigation, residual stress measurements were obtained from rail-ends which had undergone controlled amounts of surface plastic deformation using a full scale wheel-on-track simulation test rig. Results were compared with those obtained from similar investigations performed on rail ends associated with ex-service IRJs. Residual stresses were measured by neutron diffraction at the Australian Nuclear Science and Technology Organisation (ANSTO). Measurements with constant gauge volume 3x3x3 mm3 were carried in the central vertical plane on 5mm thick sliced rail samples cut by an electric discharge machine (EDM). Stress evolution at the rail ends was found to exhibit characteristics similar to those of the ex-service rails, with a compressive zone of 5mm deep that is counterbalanced by a tension zone beneath, extending to a depth of around 15mm. However, in contrast to the ex-service rails, the type of stress distribution in the test-rig deformed samples was apparently different due to the localization of load under the particular test conditions. In the latter, in contrast with clear stress evolution, there was no obvious evolution of d0. Since d0 reflects rather long-term accumulation of crystal lattice damage and microstructural changes due to service load, the loading history of the test rig samples has not reached the same level as the ex-service rails. It is concluded that the wheel-on-rail simulation rig provides the potential capability for testing the wheel-rail rolling contact conditions in rails, rail ends and insulated rail joints.

Residual stresses in rail-ends from the in-service insulated rail joints using neutron diffraction

Insulated rail joints (IRJs) are an integral part of the rail track signaling system and pose significant maintenance and replacement costs due to their low and fluctuating service lives. Failure occurs mainly in rail head region, bolt- holes of fishplates and web-holes of the rails. Propagation of cracks is influenced by the evolution of internal residual stresses in rails during rail manufacturing (hot-rolling, roller-straightening, and head-hardening process), and during service, particularly in heavy rail haul freight systems where loads are high. In this investigation, rail head accumulated residual stresses were analysed using neutron diffraction at the Australian Nuclear Science and Technology Organisation (ANSTO). Two ex-service two head-hardened rail joints damaged under different loading were examined and results were compared with those obtained from an unused rail joint reference sample in order to differentiate the stresses developed during rail manufacturing and stresses accumulated during rail service. Neutron diffraction analyses were carried out on the samples in longitudinal, transverse and vertical directions, and on 5mm thick sliceed samples cut by Electric Discharge Machining (EDM). For the rail joints from the service line, irrespective of loading conditions and in-service times, results revealed similar depth profiles of stress distribution. Evolution of residual stress fields in rails due to service was also accompanied by evidence of larger material flow based on reflected light and scanning electron microscopy studies. Stress evolution in the vicinity of rail ends was characterised by a compressive layer, approximately 5 mm deep, and a tension zone located approximately 5- 15mm below the surfaces. A significant variation of d0 with depth near the top surface was detected and was attributed to decarburization in the top layer induced by cold work. Stress distributions observed in longitudinal slices of the two different deformed rail samples were found to be similar. For the undeformed rail, the stress distributions obtained could be attributed to variations associated with thermo-mechanical history of the rail.

High pressure in situ diffraction studies of metal–hydrogen systems

“Hybrid” hydrogen storage, where hydrogen is stored in both the solid material and as a high pressure gas in the void volume of the tank can improve overall system efficiency by up to 50% compared to either compressed hydrogen or solid materials alone. Thermodynamically, high equilibrium hydrogen pressures in metal–hydrogen systems correspond to low enthalpies of hydrogen absorption–desorption. This decreases the calorimetric effects of the hydride formation–decomposition processes which can assist in achieving high rates of heat exchange during hydrogen loading—removing the bottleneck in achieving low charging times and improving overall hydrogen storage efficiency of large hydrogen stores. Two systems with hydrogenation enthalpies close to −20 kJ/mol H2 were studied to investigate the hydrogenation mechanism and kinetics: CeNi5–D2 and ZrFe2−xAlx (x = 0.02; 0.04; 0.20)–D2. The structure of the intermetallics and their hydrides were studied by in situ neutron powder diffraction at pressures up to 1000 bar and complementary X-ray diffraction. The deuteration of the hexagonal CeNi5 intermetallic resulted in CeNi5D6.3 with a volume expansion of 30.1%. Deuterium absorption filled three different types of interstices, Ce2Ni2 and Ni4 tetrahedra, and Ce2Ni3 half-octahedra and was accompanied by a valence change for Ce. Significant hysteresis was observed between deuterium absorption and desorption which profoundly decreased on a second absorption cycle. For the Al-modified Laves-type C15 ZrFe2−xAlx intermetallics, deuteration showed very fast kinetics of H/D exchange and resulted in a volume increase of the FCC unit cells of 23.5% for ZrFe1.98Al0.02D2.9(1). Deuterium content, hysteresis of H/D uptake and release, unit cell expansion and stability of the hydrides systematically change with the amount of Al content. In the deuteride D atoms exclusively occupy the Zr2(Fe,Al)2 tetrahedra. Observed interatomic distances are Zr–D = 1.98–2.11; (Fe, Al)–D = 1.70–1.75A˚ . Hydrogenation slightly increases the magnetic moment of the Fe atoms in ZrFe1.98Al0.02 and ZrFe1.96Al0.04 from 1.9 �B at room temperature for the alloy to 2.2 �B for its deuteride.

Nanostructured metal hydrides for hydrogen storage studied by in situ synchrotron and neutron diffraction

This work was focused on studies of the metal hydride materials having a potential in building hydrogen storage systems with high gravimetric and volumetric efficiencies of H storage and formed / decomposed with high rates of hydrogen exchange. In situ diffraction studies of the metal-hydrogen systems were explored as a valuable tool in probing both the mechanism of the phase-structural transformations and their kinetics. Two complementary techniques, namely Neutron Powder Diffraction (NPD) and Synchrotron X-ray diffraction (SR XRD) were utilised. High pressure in situ NPD studies were performed at D2 pressures reaching 1000 bar at the D1B diffractometer accommodated at Institute Laue Langevin, Grenoble. The data of the time resolved in situ SR XRD were collected at the Swiss Norwegian Beam Lines, ESRF, Grenoble in the pressure range up to 50 bar H2 at temperatures 20-400°C. The systems studied by NPD at high pressures included deuterated Al-modified Laves-type C15 ZrFe2-xAlx intermetallics with x = 0.02; 0.04 and 0.20 and the CeNi5-D2 system. D content, hysteresis of H uptake and release, unit cell expansion and stability of the hydrides systematically change with Al content. Deuteration exhibited a very fast kinetics; it resulted in increase of the unit cells volumes reaching 23.5 % for ZrFe1.98Al0.02D2.9(1) and associated with exclusive occupancy of the Zr2(Fe,Al)2 tetrahedra. For CeNi5 deuteration yielded a hexahydride CeNi5D6.2 (20°C, 776 bar D2) and was accompanied by a nearly isotropic volume expansion reaching 30.1% (∆a/a=10.0%; ∆c/c=7.5%). Deuterium atoms fill three different interstitial sites including Ce2Ni2, Ce2Ni3 and Ni4. Significant hysteresis was observed on the first absorption-desorption cycle. This hysteresis decreased on the absorption-desorption cycling. A different approach to the development of H storage systems is based on the hydrides of light elements, first of all the Mg-based ones. These systems were studied by SR XRD. Reactive ball milling in hydrogen (HRBM) allowed synthesis of the nanostructured Mg-based hydrides. The experimental parameters (PH2, T, energy of milling, ball / sample ratio and balls size), significantly influence rate of hydrogenation. The studies confirmed (a) a completeness of hydrogenation of Mg into MgH2; (b) indicated a partial transformation of the originally formed -MgH2 into a metastable -MgH2 (a ratio / was 3/1); (c) yielded the crystallite size for the main hydrogenation product, -MgH2, as close to 10 nm. Influence of the additives to Mg on the structure and hydrogen absorption/desorption properties and cycle behaviour of the composites was established and will be discussed in the paper.

An investigation of goethite-seeded Al(OH)3 precipitation using in situ X-ray diffraction and Rietveld-based quantitative phase analysis

An in situ X-ray diffraction investigation of goethite-seeded Al(OH)3 precipitation from synthetic Bayer liquor at 343 K has been performed. The presence of iron oxides and oxyhydroxides in the Bayer process has implications for alumina reversion, which causes significant process losses through unwanted gibbsite precipitation, and is also relevant for the nucleation and growth of scale on mild steel process equipment. The gibbsite, bayerite and nordstrandite polymorphs of Al(OH)3 precipitated from the liquor; gibbsite appeared to precipitate first, with subsequent formation of bayerite and nordstrandite. A Rietveld-based approach to quantitative phase analysis was implemented for the determination of absolute phase abundances as a function of time, from which kinetic information for the formation of the Al(OH)3 phases was determined.

Optics of the human eye in diabetes

This study compared optics of eyes in people with diabetes with those age-balanced controls. Relative to the control group, the diabetes group demonstrated greater lens thickness, more curved lens shapes, smaller lens diameters, higher light scatter, greater lens yellowing, and poorer focusing ability. While the optics of the people with diabetes made them appear as older eyes than those of people of the same age without diabetes, the differences did not increase significantly with age. It was concluded that age-related changes in eyes of people with diabetes need not be accelerated if the diabetes is well controlled.

Structural characterization of hydrogen peroxide‐oxidized anthracites by X-ray diffraction, Fourier transform infrared spectroscopy, and Raman spectra

The structural characteristics of raw coal and hydrogen peroxide (H2O2)-oxidized coals were investigated using scanning electron microscopy, X-ray diffraction (XRD), Raman spectra, and Fourier transform infrared (FT-IR) spectroscopy. The results indicate that the derivative coals oxidized by H2O2 are improved noticeably in aromaticity and show an increase first and then a decrease up to the highest aromaticity at 24 h. The stacking layer number of crystalline carbon decreases and the aspect ratio (width versus stacking height) increases with an increase in oxidation time. The content of crystalline carbon shows the same change tendency as the aromaticity measured by XRD. The hydroxyl bands of oxidized coals become much stronger due to an increase in soluble fatty acids and alcohols as a result of the oxidation of the aromatic and aliphatic C‐H bonds. In addition, the derivative coals display a decrease first and then an increase in the intensity of aliphatic C‐H bond and present a diametrically opposite tendency in the aromatic C‐H bonds with an increase in oxidation time. There is good agreement with the changes of aromaticity and crystalline carbon content as measured by XRD and Raman spectra. The particle size of oxidized coals (<200 nm in width) shows a significant decrease compared with that of raw coal (1 μm). This study reveals that the optimal oxidation time is ∼24 h for improving the aromaticity and crystalline carbon content of H2O2-oxidized coals. This process can help us obtain superfine crystalline carbon materials similar to graphite in structure.

J.W.Lindt’s Colonial man and Aborigine image from the GRAFTON ALBUM : “On chemistry and optics all does not depend, art must with these in triple union blend”

J.W.Lindt’s Colonial man and Aborigine image from the GRAFTON ALBUM: “On chemistry and optics all does not depend, art must with these in triple union blend” (text from J.W. Lindt’s photographic backing card) In this paper, I follow an argument that Lindt held a position in his particular colonial environment where he was simultaneously both an insider and an outsider and that such a position may be considered prerequisite in stimulating exchange. A study of the transition of J.W. Lindt in Grafton, N.S.W. in the 1860s from a traveller to a migrant and subsequently to a professional photographer, as well as Lindt’s photographic career, which evolved through strategic action and technical approaches to photography, bears witness to his cultural relativity. One untitled photograph from this period of work constructs a unique commentary of Australian colonial life that illustrates a non-hegemonic position, particularly as it was included in one of the first albums of photographs of Aborigines that Lindt gifted to an illustrious person (in this case the Mayor of Grafton). As in his other studio constructions, props and backdrops were arranged and sitters were positioned with care, but this photograph is the only one in the album that includes a non-Aborigine in a relationship to an Aborigine. An analysis of the props, technical details of the album and the image suggests a reconciliatory aspect that thwarts the predominant attitudes towards Aborigines in the area at that time.

Miniscleral lens wear influences corneal curvature and optics

Purpose Transient changes in corneal topography associated with soft and conventional or reverse geometry rigid contact lens wear have been well documented; however, only a few studies have examined the influence of scleral contact lens wear upon the cornea. Therefore, in this study, we examined the influence of modern miniscleral contact lenses, which land entirely on the sclera and overlying tissues, upon anterior corneal curvature and optics. Methods Anterior corneal topography and elevation data were acquired using Scheimpflug imaging (Pentacam HR, Oculus) immediately prior to and following 8 hours of miniscleral contact lens wear in 15 young healthy adults (mean age 22 ± 3 years, 8 East Asian, 7 Caucasian) with normal corneae. Corneal diurnal variations were accounted for using data collected on a dedicated measurement day without contact lens wear. Corneal clearance was quantified using an optical coherence tomographer (RS-3000, Nidek) following lens insertion and after 8 hours of lens wear. Results Although corneal clearance was maintained throughout the 8 hour lens wear period, significant corneal flattening (up to 0.08 ± 0.04 mm) was observed, primarily in the superior mid-peripheral cornea, which resulted in a slight increase in against-the-rule corneal astigmatism (mean +0.02/-0.15 x 94 for an 8 mm diameter). Higher order aberration terms of horizontal coma, vertical coma and spherical aberration all underwent significant changes for an 8 mm corneal diameter (p ≤ 0.01), which typically resulted in a decrease in RMS error values (mean change in total higher order RMS -0.035 ± 0.046 µm for an 8 mm diameter). There was no association between the magnitude of change in central or mid-peripheral corneal clearance during lens wear and the observed changes in corneal curvature (p > 0.05). However, Asian participants displayed a significantly greater reduction in corneal clearance (p = 0.04) and greater superior-nasal corneal flattening compared to Caucasians (p = 0.048). Conclusions Miniscleral contact lenses that vault the cornea induce significant changes in anterior corneal surface topography and higher order aberrations following 8 hours of lens wear. The region of greatest corneal flattening was observed in the superior-nasal mid-periphery, more so in Asian participants. Practitioners should be aware that corneal measurements obtained following miniscleral lens removal may mask underlying corneal steepening.