Reconstructing 3D x-ray CT images of polymer gel dosimeters using the zero-scan method

In this study x-ray CT has been used to produce a 3D image of an irradiated PAGAT gel sample, with noise-reduction achieved using the ‘zero-scan’ method. The gel was repeatedly CT scanned and a linear fit to the varying Hounsfield unit of each pixel in the 3D volume was evaluated across the repeated scans, allowing a zero-scan extrapolation of the image to be obtained. To minimise heating of the CT scanner’s x-ray tube, this study used a large slice thickness (1 cm), to provide image slices across the irradiated region of the gel, and a relatively small number of CT scans (63), to extrapolate the zero-scan image. The resulting set of transverse images shows reduced noise compared to images from the initial CT scan of the gel, without being degraded by the additional radiation dose delivered to the gel during the repeated scanning. The full, 3D image of the gel has a low spatial resolution in the longitudinal direction, due to the selected scan parameters. Nonetheless, important features of the dose distribution are apparent in the 3D x-ray CT scan of the gel. The results of this study demonstrate that the zero-scan extrapolation method can be applied to the reconstruction of multiple x-ray CT slices, to provide useful 2D and 3D images of irradiated dosimetry gels.

An X chromosome association scan of the Norfolk Island genetic isolate provides evidence for a novel migraine susceptibility locus at Xq12

Migraine is a common and debilitating neurovascular disorder with a complex envirogenomic aetiology. Numerous studies have demonstrated a preponderance of women affected with migraine and previous pedigree linkage studies in our laboratory have identified susceptibility loci on chromosome Xq24-Xq28. In this study we have used the genetic isolate of Norfolk Island to further analyse the X chromosome for migraine susceptibility loci. An association approach was employed to analyse 14,124 SNPs spanning the entire X chromosome. Genotype data from 288 individuals comprising a large core-pedigree, of which 76 were affected with migraine, were analysed. Although no SNP reached chromosome-wide significance (empirical α = 1×10−5) ranking by P-value revealed two primary clusters of SNPs in the top 25. A 10 SNP cluster represents a novel migraine susceptibility locus at Xq12 whilst a 11 SNP cluster represents a previously identified migraine susceptibility locus at Xq27. The strongest association at Xq12 was seen for rs599958 (OR = 1.75, P = 8.92×10−4), whilst at Xq27 the strongest association was for rs6525667 (OR = 1.53, P = 1.65×10−4). Further analysis of SNPs at these loci was performed in 5,122 migraineurs from the Women’s Genome Health Study and provided additional evidence for association at the novel Xq12 locus (P<0.05). Overall, this study provides evidence for a novel migraine susceptibility locus on Xq12. The strongest effect SNP (rs102834, joint P = 1.63×10−5) is located within the 5′UTR of the HEPH gene, which is involved in iron homeostasis in the brain and may represent a novel pathway for involvement in migraine pathogenesis.

A genome-wide scan provides evidence for loci influencing a severe heritable form of common migraine

Migraine is a prevalent neurovascular disease with a significant genetic component. Linkage studies have so far identified migraine susceptibility loci on chromosomes 1, 4, 6, 11, 14, 19 and X. We performed a genome-wide scan of 92 Australian pedigrees phenotyped for migraine with and without aura and for a more heritable form of “severe” migraine. Multipoint non-parametric linkage analysis revealed suggestive linkage on chromosome 18p11 for the severe migraine phenotype (LOD*=2.32, P=0.0006) and chromosome 3q (LOD*=2.28, P=0.0006). Excess allele sharing was also observed at multiple different chromosomal regions, some of which overlap with, or are directly adjacent to, previously implicated migraine susceptibility regions. We have provided evidence for two loci involved in severe migraine susceptibility and conclude that dissection of the “migraine” phenotype may be helpful for identifying susceptibility genes that influence the more heritable clinical (symptom) profiles in affected pedigrees. Also, we concluded that the genetic aetiology of the common (International Headache Society) forms of the disease is probably comprised of a number of low to moderate effect susceptibility genes, perhaps acting synergistically, and this effect is not easily detected by traditional single-locus linkage analyses of large samples of affected pedigrees.

Electrochemically-induced TCNQ/Mn TCNQ 2 (H2O) 2 (TCNQ= 7, 7, 8, 8-Tetracyanoquinodimethane) solid-solid interconversion : two voltammetrically distinct processes that allow selective generation of nanofiber or nanorod network morphologies

Unlike the case with other divalent transition metal M\[TCNQ](2)(H(2)O)(2) (M = Fe, Co, Ni) analogues, the electrochemically induced solid-solid phase interconversion of TCNQ microcrystals (TCNQ = 7,7,8,8-tetracyanoquinodimethane) to Mn\[TCNQ](2)(H(2)O)(2) occurs via two voltammetrically distinct, time dependent processes that generate the coordination polymer in nanofiber or rod-like morphologies. Careful manipulation of the voltammetric scan rate, electrolysis time, Mn(2+)((aq)) concentration, and the method of electrode modification with solid TCNQ allows selective generation of either morphology. Detailed ex situ spectroscopic (IR, Raman), scanning electron microscopy (SEM), and X-ray powder diffraction (XRD) characterization clearly establish that differences in the electrochemically synthesized Mn-TCNQ material are confined to morphology. Generation of the nanofiber form is proposed to take place rapidly via formation and reduction of a Mn-stabilized anionic dimer intermediate, \[(Mn(2+))(TCNQ-TCNQ)(2)(*-)], formed as a result of radical-substrate coupling between TCNQ(*-) and neutral TCNQ, accompanied by ingress of Mn(2+) ions from the aqueous solution at the triple phase TCNQ/electrode/electrolyte boundary. In contrast, formation of the nanorod form is much slower and is postulated to arise from disproportionation of the \[(Mn(2+))(TCNQ-TCNQ)(*-)(2)] intermediate. Thus, identification of the time dependent pathways via the solid-solid state electrochemical approach allows the crystal size of the Mn\[TCNQ](2)(H(2)O)(2) material to be tuned and provides new mechanistic insights into the formation of different morphologies.

A feasibility study of multislice x-ray CT imaging of gel dosimeters using the “zero scan” method

This study extends the ‘zero scan’ method for CT imaging of polymer gel dosimeters to include multi-slice acquisitions. Multi slice CT images consisting of 24 slices of 1.2 mm thickness were acquired of an irradiated polymer gel dosimeter, and processed with the zero scan technique. The results demonstrate that zero scan based gel readout can be successfully applied to generate a three dimensional image of the irradiated gel field. Compared to the raw CT images the processed figures and cross gel profiles demonstrated reduced noise and clear visibility of the penumbral region. Moreover these improved results further highlight the suitability of this method in volumetric reconstruction with reduced CT data acquisition per slice. This work shows that 3D volumes of irradiated polymer gel dosimeters can be acquired and processed with x-ray CT.

Measurement of the first neutron diffraction peak of D2O flowing in a 2 mm diameter aluminium tube as a function of temperature

A pilot experiment was performed using the WOMBAT powder diffraction instrument at ANSTO in which the first neutron diffraction peak (Q0) was measured for D2O flowing in a 2 mm internal diameter aluminium tube. Measurements of Q0 were made at -9, 4.3, 6.9, 12, 18.2 and 21.5 °C. The D2O was circulated using a siphon with water in the lower reservoir returned to the upper reservoir using a small pump. This enabled stable flow to be maintained for several hours. For example, if the pump flow increased slightly, the upper reservoir level rose, increasing the siphon flow until it matched the return flow. A neutron wavelength of 2.4 Å was used and data integrated over 60 minutes for each temperature. A jet of nitrogen from a liquid N2 Dewar was directed over the aluminium tube to vary water temperature. After collection of the data, the d spacing of the aluminium peaks was used to calculate the temperature of the aluminium within the neutron beam and therefore was considered to be an accurate measure of water temperature within the beam. Sigmaplot version 12.3 was used to fit a Weibull five parameter peak fit to the first neutron diffraction peak. The values of Q0 obtained in this experiment showed an increase with temperature consistent with data in the literature [1] but were consistently higher than published values for bulk D20. For example at 21.5 °C we obtained a value of 2.008 Å-1 for Q0 compared to a literature value of 1.988 Å-1 for bulk D2O at 20 °C, a difference of 1%. Further experiments are required to see if this difference is real or artifactual.

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.

Using pulse transit delay in Z-scan to discriminate between excited-state absorption and other nonlinear processes in ZnO nanocones

We report a new approach that uses the single beam Z-scan technique, to discriminate between excited state absorption (ESA) and two and three photon nonlinear absorption. By measuring the apparent delay or advance of the pulse in reaching the detector, the nonlinear absorption can be unambiguously identified as either instantaneous or transient. The simple method does not require a large range of input fluences or sophisticated pulse-probe experimental apparatus. The technique is easily extended to any absorption process dependent on pulse width and to nonlinear refraction measurements. We demonstrate in particular, that the large nonlinear absorption in ZnO nanocones when exposed to nanosecond 532 nm pulses, is due mostly to ESA, not pure two-photon absorption.

Organo-LDH synthesized via tricalcium aluminate hydration in the present of Na-dodecylbenzenesulfate aqueous solution and subsequent investigated by near-infrared and mid-infrared

Na-dodecylbenzenesulfate (SDBS), a natural anionic surfactant, has been successfully intercalated into a Ca based LDH host structure during tricalcium aluminate hydration in the presence of SDBS aqueous solution (CaAl-SDBS-LDH). The resulting product was characterized by powder X-ray diffraction (XRD), mid-infrared (MIR) spectroscopy combined with near-infrared (NIR) spectroscopy technique, thermal analysis (TG–DTA) and scan electron microscopy (SEM). The XRD results revealed that the interlayer distance of resultant product was expanded to 30.46 Å. MIR combined with NIR spectra offered an effective method to illustrate this intercalation. The NIR spectra (6000–5500 cm−1) displayed prominent bands to expound SDBS intercalated into hydration product of C3A. And the bands around 8300 cm−1 were assigned to the second overtone of the first fundamental of CH stretching vibrations of SDBS. In addition, thermal analysis showed that the dehydration and dehydroxylation took place at ca. 220 °C and 348 °C, respectively. The SEM results appeared approximately hexagonal platy crystallites morphology for CaAl-SDBS-LDH, with particle size smaller and thinner.

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.