The environment of iron in silicate glasses

Iron species in glass are vital to applications such as solar control, and greater understanding of these species is required. Redox, coordination, distribution and environment of iron in alkali-alkaline earth-silica glasses containing 0-5 molar % Fe203 have been studied using a multi-technique approach. Wet chemical analysis provided values of the Fee+/EFe redox ratio and these are in agreement with those obtained from optical and Mössbauer techniques over a wide range of glass compositions and Fe203 contents. The Fee+/EFe ratio is independent of iron content in the glasses studied, provided that melting conditions allow sufficient equilibration with the furnace atmosphere. As iron content increases, Fe-Fe near-neighbour interactions have an increasing influence on measured properties. Mössbauer parameters indicate a wider range of site occupancies by Fe 2+ and Fe 3+ at low iron contents. Electron spin resonance suggests some clustering of Fe ions even at low iron concentrations. The amount of clustering is proportional to the square of the molar Fe203 content. Increasing alkali / alkaline earth ionic radius ratio promotes clustering at all Fe203 contents. The effects of alkali and alkaline earth ions on the redox, distribution, coordination and environment of Fe ions in these glasses generally fall into two behavioural categories which have been termed "collective" and "selective". Collective behaviour occurs when alkali and alkaline earth ions have similar effects on a property and the overall effect is cumulative. This is characterised by proportionality with theoretical optical basicity of the glass. Many parameters associated with Fe 2+ ions fall into this category. Selective behaviour occurs when alkali and alkaline earth ions have opposing effects on a property, suggesting competition or selectivity between ion types. This is characterised by proportionality with the alkali / alkaline earth ionic radius ratio. The redox ratio and several parameters associated with the clustering, coordination and environment of Fe 3+ ions fall into this category. Glasses containing MgO can exhibit behaviour dissimilar to the other alkaline earth oxides; molar volume, redox, coordination and clustering are affected. These phenomena may be due to some Mg 2+ ions occupying tetrahedral sites

X-ray Fluorescence Analysis of Feldspars and Silicate Glass: Effects of Melting Time on Fused Bead Consistency and Volatilisation

Reproducible preparation of lithium tetraborate fused beads for XRF analysis of glass and mineral samples is of paramount importance for analytical repeatability. However, as with all glass melting processes, losses due to volatilisation must be taken into account and their effects are not negligible. Here the effects of fused bead melting time have been studied for four Certified Reference Materials (CRM’s: three feldspars, one silicate glass), in terms of their effects on analytical variability and volatilisation losses arising from fused bead preparation. At melting temperatures of 1065 °C, and for feldspar samples, fused bead melting times shorter than approximately 25 min generally gave rise to a greater deviation of the XRF-analysed composition from the certified composition. This variation might be due to incomplete fusion and/or fused bead inhomogeneity but further research is needed. In contrast, the shortest fused bead melting time for the silicate glass CRM gave an XRF-analysed composition closer to the certified values than longer melting times. This may suggest a faster rate of glass-in-glass dissolution and homogenization during fused bead preparation. For all samples, longer melting times gave rise to greater volatilisation losses (including sulphates and halides) during fusion. This was demonstrated by a linear relationship between SO3 mass loss and time1/2, as predicted by a simple diffusion-based model. Iodine volatilisation displays a more complex relationship, suggestive of diffusion plus additional mechanisms. This conclusion may have implications for vitrification of iodine-bearing radioactive wastes. Our research demonstrates that the nature of the sample material impacts on the most appropriate fusion times. For feldspars no less than ~25 min and no more than ~60 min of fusion at 1065 °C, using Li2B4O7 as the fusion medium and in the context of feldspar samples and the automatic fusion equipment used here, strikes an acceptable (albeit non-ideal) balance between the competing factors of fused bead quality, analytical consistency and mitigating volatilisation losses. Conversely, for the silicate glass sample, shorter fusion times of less than ~30 min under the same conditions provided more accurate analyses whilst limiting volatile losses

Reliability and Validity of the Early Years Physical Activity Questionnaire (EY-PAQ).

Measuring physical activity (PA) and sedentary time (ST) in young children (<5 years) is complex. Objective measures have high validity but require specialist expertise, are expensive, and can be burdensome for participants. A proxy-report instrument for young children that accurately measures PA and ST is needed. The aim of this study was to assess the reliability and validity of the Early Years Physical Activity Questionnaire (EY-PAQ). In a setting where English and Urdu are the predominant languages spoken by parents of young children, a sample of 196 parents and their young children (mean age 3.2 ± 0.8 years) from Bradford, UK took part in the study. A total of 156 (79.6%) questionnaires were completed in English and 40 (20.4%) were completed in transliterated Urdu. A total of 109 parents took part in the reliability aspect of the study, which involved completion of the EY-PAQ on two occasions (7.2 days apart; standard deviation (SD) = 1.1). All 196 participants took part in the validity aspect which involved comparison of EY-PAQ scores against accelerometry. Validty anaylsis used all data and data falling with specific MVPA and ST boundaries. Reliability was assessed using intra-class correlations (ICC) and validity by Bland⁻Altman plots and rank correlation coefficients. The test re-test reliability of the EY-PAQ was moderate for ST (ICC = 0.47) and fair for moderate-to-vigorous physical activity (MVPA)(ICC = 0.35). The EY-PAQ had poor agreement with accelerometer-determined ST (mean difference = -87.5 min·day-1) and good agreement for MVPA (mean difference = 7.1 min·day-1) limits of agreement were wide for all variables. The rank correlation coefficient was non-significant for ST (rho = 0.19) and significant for MVPA (rho = 0.30). The EY-PAQ has comparable validity and reliability to other PA self-report tools and is a promising population-based measure of young children's habitual MVPA but not ST. In situations when objective methods are not possible for measurement of young children's MVPA, the EY-PAQ may be a suitable alternative but only if boundaries are applied

Digitally controlled converter with an adaptive step size for maximum power point tracking for photovoltaic applications

Maximum power point trackers (MPPTs) are required to ensure optimum utilization of photovoltaic (PV) arrays in renewable energy systems, both as stand-alone and as supplementary sources of energy. In this paper, a MPPT algorithm is presented based on the perturb and observe (P & O) approach, implemented with an adaptive perturbation step size to allow fast convergence to the required operating point

Complex magnetic ordering in the oxide selenide Sr2Fe3Se2O3

Sr2Fe3Se2O3 is a localised-moment iron oxide selenide in which two unusual coordinations for Fe2+ ions form two sublattices in a 2:1 ratio. In the paramagnetic region at room temperature the compound adopts the crystal structure first reported for Sr2Co3S2O3, crystallising in space group Pbam with a = 7.8121 Å, b = 10.2375 Å, c = 3.9939 Å and Z = 2. The sublattice occupied by two thirds of the iron ions (Fe2 site) is formed by a network of distorted mer-[FeSe3O3] octahedra linked via shared Se2 edges and O vertices forming layers, which connect to other layers by shared Se vertices. As shown by magnetometry, neutron powder diffraction and Mössbauer spectroscopy measurements, these moments undergo long range magnetic ordering below TN1 = 118 K, initially adopting a magnetic structure with a propagation vector (½–δ, 0, ½) (0 ≤ ≤ 0.1) which is incommensurate with the nuclear structure and described in the Pbam1’(a01/2)000s magnetic superspace group, until at 92 K (TINC) there is a first order lock-in transition to a structure in which these Fe2 moments form a magnetic structure with a propagation vector (½ , 0, ½) which may be modelled using a 2a × b × 2c expansion of the nuclear cell in space group 36.178 Bab21m (BNS notation). Below TN2 = 52 K the remaining third of the Fe2+ moments (Fe1 site) which are in a compressed trans-[FeSe4O2] octahedral environment undergo long range ordering, as is evident from the magnetometry, the Mössbauer spectra and the appearance of new magnetic Bragg peaks in the neutron diffractograms. The ordering of the second set of moments on the Fe1 sites results in a slight re-orientation of the majority moments on the Fe2 sites. The magnetic structure at 1.5 K is described by a 2a × 2b × 2c expansion of the nuclear cell in space group 9.40 Iab (BNS notation)

Magnetic interactions in cubic-, hexagonal- and trigonal barium iron oxide fluoride, BaFeO2F

57Fe Mössbauer spectra have been recorded from the hexagonal (6H)- and trigonal (15R)- modifications of BaFeO2F and are compared with those previously recorded from the cubic form of BaFeO2F. The spectra, recorded over a temperature range from 15 to 650K show that all of the iron in all the compounds is in the Fe3+ state. Spectra from the 6H- and 15R- modifications were successfully fitted with components that were related to the Fe(1) and Fe(2) structural sites in the 6H variant and to the Fe(1), Fe(2) and Fe(3) structural sites in the 15R form. The magnetic ordering temperatures were determined as 597±3K for 6H-BaFeO2F and 636±3K for 15R-BaFeO2F. These values are surprisingly close to the value of 645±5K determined for the cubic form. The magnetic interactions in the three forms are compared with a view to explaining this similarity of magnetic ordering temperature. Keywords : Mossbauer barium iron oxide fluorid

Structural changes in FeOx/γ-Al2O3 catalysts during ethylbenzene dehydrogenation

The structural changes that occur in a FeOx/γ-Al2O3 catalyst during the dehydrogenation of ethylbenzene in a fluidized CREC Riser Simulator have been investigated. Chemical and morphological changes are observed to take place as a result of reaction. Electron microscopy reveals the formation of needle-like alumina structures apparently enclosing iron oxide particles. The formation of such structures at relatively low temperatures is unexpected and has not previously been reported. Additionally, X-ray diffraction and Mössbauer spectroscopy confirmed the reduction of the oxidation state of iron, from Fe2O3 (haematite) to Fe3O4 (magnetite). Iron carbides, Fe3C and ɛ-Fe2C, were detected by electron microscopy through electron diffraction and lattice fringes analysis. Carbon deposition (coking) on the catalyst surface also occurs. The observed structural changes are likely to be closely correlated with the catalytic properties of the materials, in particular with catalyst deactivation, and thereby provide important avenues for future study of this industrially important reaction. Fe2O3/Al2O3 catalyst undergoes chemical and morphological changes during ethylbenzene dehydrogenation forming Al2O3 needles which appear to contain reduced Fe3O4 particles. Fe3C also forms during reaction

Integrated waveguide-coupled terahertz microcavity resonators

We demonstrate integrated square terahertz microcavity resonators side coupled to waveguides. We present the microcavity transmission spectra for different resonator sizes and coupling strengths. The measured quality factors due to external coupling and cavity loss are found to be between 40 and 90 and between 30 and 40, respectively, for cavity resonance frequencies between 1.077 and 1.331 THz.Peer reviewedElectrical and Computer Engineerin

Visualization methods for understanding the dynamic electroadhesion phenomenon

Experimental investigation into the surface potential and electric field visualization of an electroadhesion system is presented for understanding the dynamic electroadhesion phenomenon. The indirect experimental approach has been based on measuring surface potentials on the surface of an electroadhesive pad by an electrostatic voltmeter. The direct approach has been based on charging and discharging the electroadhesive pad in a viscous oil mixed with lightweight particles. The visualization of the dynamic field distribution of electroadhesive pads can be a useful method to understand the dynamic electroadhesion phenomenon. In addition, indication of different field distributions of different pad geometries can be obtained through the method demonstrated here. Furthermore, the method is useful for instructors or lecturers to showcase or teach the dynamic electroadhesion phenomenon