222 resultados para Metal insulator transition


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Glass transition temperature of spaghetti sample was measured by thermal and rheological methods as a function of water content.

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The identification of attractors is one of the key tasks in studies of neurobiological coordination from a dynamical systems perspective, with a considerable body of literature resulting from this task. However, with regards to typical movement models investigated, the overwhelming majority of actions studied previously belong to the class of continuous, rhythmical movements. In contrast, very few studies have investigated coordination of discrete movements, particularly multi-articular discrete movements. In the present study, we investigated phase transition behavior in a basketball throwing task where participants were instructed to shoot at the basket from different distances. Adopting the ubiquitous scaling paradigm, throwing distance was manipulated as a candidate control parameter. Using a cluster analysis approach, clear phase transitions between different movement patterns were observed in performance of only two of eight participants. The remaining participants used a single movement pattern and varied it according to throwing distance, thereby exhibiting hysteresis effects. Results suggested that, in movement models involving many biomechanical degrees of freedom in degenerate systems, greater movement variation across individuals is available for exploitation. This observation stands in contrast to movement variation typically observed in studies using more constrained bi-manual movement models. This degenerate system behavior provides new insights and poses fresh challenges to the dynamical systems theoretical approach, requiring further research beyond conventional movement models.

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Purpose: In the present work we consider our (in progress) spectroscopy study of zinc and iron phosphates under the influence external high pressure to determine zinc ion change coordination from tetrahedral to octahedral (or hexahedral) structure.----- Design/methodology/approach: The standard equipment is the optical high pressure cell with diamond (DAC). The DAC is assembled and then vibrational or electronic spectra are collected by mounting the cell in an infrared, Raman, EXAFS or UV-visible spectrometer.----- Findings: Mechanism by which zinc and iron methaphosphate material is transformed to glassy meta-phosphate is enhancing mechanical properties of tribofilm. The two decades of intensive study demonstrates that Zn (II) and Fe (III) ions participate to cross-link network under friction, hardening the phosphate.----- Research limitations/implications: Transition metal atoms with d orbital have flexible coordination numbers, for example zinc acts as a cross-linking agent increasing hardness, by changing coordination from tetrahedral to octahedral. Perhaps the external pressure effect on the [Zn–(O-P-)4 ] complex causes a transformation to an [Zn –(O-P-)6] grouping.----- Originality/value: This paper analyses high-pressure spectroscopy which has been applied for the investigation of 3D transition metal ions in solids. When studying pressure effects on coordination compounds structure, we can expect changes in ground electronic state (spin-crossovers), electronic spectra due to structural distortions (piezochromism), and changes in the ligand field causing shifts in the electronic transitions.

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Traditional ceramic separation membranes, which are fabricated by applying colloidal suspensions of metal hydroxides to porous supports, tend to suffer from pinholes and cracks that seriously affect their quality. Other intrinsic problems for these membranes include dramatic losses of flux when the pore sizes are reduced to enhance selectivity and dead-end pores that make no contribution to filtration. In this work, we propose a new strategy for addressing these problems by constructing a hierarchically structured separation layer on a porous substrate using large titanate nanofibers and smaller boehmite nanofibers. The nanofibers are able to divide large voids into smaller ones without forming dead-end pores and with the minimum reduction of the total void volume. The separation layer of nanofibers has a porosity of over 70% of its volume, whereas the separation layer in conventional ceramic membranes has a porosity below 36% and inevitably includes dead-end pores that make no contribution to the flux. This radical change in membrane texture greatly enhances membrane performance. The resulting membranes were able to filter out 95.3% of 60-nm particles from a 0.01 wt % latex while maintaining a relatively high flux of between 800 and 1000 L/m2·h, under a low driving pressure (20 kPa). Such flow rates are orders of magnitude greater than those of conventional membranes with equal selectivity. Moreover, the flux was stable at approximately 800 L/m2·h with a selectivity of more than 95%, even after six repeated runs of filtration and calcination. Use of different supports, either porous glass or porous alumina, had no substantial effect on the performance of the membranes; thus, it is possible to construct the membranes from a variety of supports without compromising functionality. The Darcy equation satisfactorily describes the correlation between the filtration flux and the structural parameters of the new membranes. The assembly of nanofiber meshes to combine high flux with excellent selectivity is an exciting new direction in membrane fabrication.

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Fatigue and overwork are problems experienced by numerous employees in many industry sectors. Focusing on improving work-life balance can frame the ‘problem’ of long work hours to resolve working time duration issues. Flexible work options through re-organising working time arrangements is key to developing an organisational response for delivering work-life balance and usually involves changing the internal structure of work time. This study examines the effect of compressed long weekly working hours and the consequent ‘long break’ on work-life balance. Using Spillover theory and Border theory, this research considers organisational and personal determinants of overwork and fatigue. It concludes compressed long work hours with a long break provide better work-life balance. Further, a long break allows gaining ‘personal time’ and overcoming fatigue.

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The degradation of high voltage electrical insulation is a prime factor that can significantly influence the reliability performance and the costs of maintaining high voltage electricity networks. Little information is known about the system of localized degradation from corona discharges on the relatively new silicone rubber sheathed composite insulators that are now being widely used in high voltage applications. This current work focuses on the fundamental principles of electrical corona discharge phenomena to provide further insights to where damaging surface discharges may localize and examines how these discharges may degrade the silicone rubber material. Although water drop corona has been identified by many authors as a major cause of deterioration of silicone rubber high voltage insulation until now no thorough studies have been made of this phenomenon. Results from systematic measurements taken using modern digital instrumentation to simultaneously record the discharge current pulses and visible images associated with corona discharges from between metal electrodes, metal electrodes and water drops, and between waters drops on the surface of silicone rubber insulation, using a range of 50 Hz voltages are inter compared. Visual images of wet electrodes show how water drops can play a part in encouraging flashover, and the first reproducible visual images of water drop corona at the triple junction of water air and silicone rubber insulation are presented. A study of the atomic emission spectra of the corona produced by the discharge from its onset up to and including spark-over, using a high resolution digital spectrometer with a fiber optic probe, provides further understanding of the roles of the active species of atoms and molecules produced by the discharge that may be responsible for not only for chemical changes of insulator surfaces, but may also contribute to the degradation of the metal fittings that support the high voltage insulators. Examples of real insulators and further work specific to the electrical power industry are discussed. A new design concept to prevent/reduce the damaging effects of water drop corona is also presented.

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Ceramic membranes are of particular interest in many industrial processes due to their ability to function under extreme conditions while maintaining their chemical and thermal stability. Major structural deficiencies under conventional fabrication approach are pin-holes and cracks, and the dramatic losses of flux when pore sizes are reduced to enhance selectivity. We overcome these structural deficiencies by constructing hierarchically structured separation layer on a porous substrate using larger titanate nanofibres and smaller boehmite nanofibres. This yields a radical change in membrane texture. The differences in the porous supports have no substantial influences on the texture of resulting membranes. The membranes with top layer of nanofibres coated on different porous supports by spin-coating method have similar size of the filtration pores, which is in a range of 10–100 nm. These membranes are able to effectively filter out species larger than 60 nm at flow rates orders of magnitude greater than conventional membranes. The retention can attain more than 95%, while maintaining a high flux rate about 900 L m-2 h. The calcination after spin-coating creates solid linkages between the fibres and between fibres and substrate, in addition to convert boehmite into -alumina nanofibres. This reveals a new direction in membrane fabrication.

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Titanate nanofibers with two formulas, Na2Ti3O7 and Na1.5H0.5Ti3O7, respectively, exhibit ideal properties for removal of radioactive and heavy metal ions in wastewater, such as Sr2+ , Ba2+ (as substitute of 226Ra2+), and Pb2+ ions. These nanofibers can be fabricated readily by a reaction between titania and caustic soda and have structures in which TiO6 octahedra join each other to form layers with negative charges; the sodium cations exist within the interlayer regions and are exchangeable. They can selectively adsorb the bivalent radioactive ions and heavy metal ions from water through ion exchange process. More importantly, such sorption finally induces considerable deformation of the layer structure, resulting in permanent entrapment of the toxic bivalent cations in the fibers so that the toxic ions can be safely deposited. This study highlights that nanoparticles of inorganic ion exchangers with layered structure are potential materials for efficient removal of the toxic ions from contaminated water.

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Near-infrared spectroscopy is a somewhat unutilised technique for the study of minerals. The technique has the ability to determine water content, hydroxyl groups and transition metals. In this paper we show the application of NIR spectroscopy to the study of selected minerals. The structure and spectral properties of two Cu-tellurite minerals graemite and teineite are compared with bismuth containing tellurite mineral smirnite by the application of NIR and IR spectroscopy. The position of Cu2+ bands and their splitting in the electronic spectra of tellurites are in conformity with octahedral geometry distortion. The spectral pattern of smirnite resembles graemite and the observed band at 10855 cm-1 with a weak shoulder at 7920 cm-1 is identified as due to Cu2+ ion. Any transition metal impurities may be identified by their bands in this spectral region. Three prominent bands observed in the region of 7200-6500 cm-1 are the overtones of water whilst the weak bands observed near 6200 cm-1in tellurites may be attributed to the hydrogen bonding between (TeO3)2- and H2O. The observation of a number of bands centred at around 7200 cm-1 confirms molecular water in tellurite minerals. A number of overlapping bands in the low wavenumbers 4500-4000 cm-1 is the result of combinational modes of (TeO3)2−ion. The appearance of the most intense peak at 5200 cm-1 with a pair of weak bands near 6000 cm-1 is a common feature in all the spectra and is related to the combinations of OH vibrations of water molecules, and bending vibrations ν2 (δ H2O). Bending vibrations δ H2O observed in the IR spectra shows a single band for smirnite at 1610 cm-1. The resolution of this band into number of components is evidenced for non-equivalent types of molecular water in graemite and teineite. (TeO3)2- stretching vibrations are characterized by three main absorptions at 1080, 780 and 695 cm-1.

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Two series of novel ruthenium bipyridyl dyes incorporating sulfur-donor bidentate ligands with general formula \[Ru(R-bpy)2C2N2S2] and \[Ru(R-bpy)2(S2COEt)]\[NO3] (where R =H, CO2Et, CO2H; C2N2S2 = cyanodithioimidocarbonate and S2COEt = ethyl xanthogenate) have been synthesized and characterized spectroscopically, electrochemically and computationally. The acid derivatives in both series (C2N2S2 3 and S2COEt 6) were used as a photosensitizer in a dye-sensitized solar cell (DSSC) and the incident photo-to-current conversion efficiency (IPCE), overall efficiency (_) and kinetics of the dye/TiO2 system were investigated. It was found that 6 gave a higher efficiency cell than 3 despite the latter dye’s more favorable electronic properties, such as greater absorption range, higher molar extinction coefficient and large degree of delocalization of the HOMO. The transient absorption spectroscopy studies revealed that the recombination kinetics of 3 were unexpectedly fast, which was attributed to the terminal CN on the ligand binding to the TiO2, as evidenced by an absorption study of R =H and CO2Et dyes sensitized on TiO2, and hence leading to a lower efficiency DSSC.

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Four nickel carbonate-bearing minerals from Australia have been investigated to study the effect of Ni for Mg substitution. The spectra of nullaginite, zaratite, widgiemoolthalite and takovite show three main features in the range of 26,720–25,855 cm−1 (ν1-band), 15,230–14,740 cm−1 (ν2-band) and 9,200–9,145 cm−1 (ν3-band) which are characteristic of divalent nickel in six-fold coordination. The Crystal Field Stabilization Energy (CFSE) of Ni2+ in the four carbonates is calculated from the observed 3A2g(3F) → 3T2g(3F) transition. CFSE is dependent on mineralogy, crystallinity and chemical composition (Al/Mg-content). The splitting of the ν1- and ν3-bands and non-Gaussian shape of ν3-band in the minerals are the effects of Ni-site distortion from regular octahedral. The effect of structural cation substitutions (Mg2+, Ni2+, Fe2+ and trivalent cations, Al3+, Fe3+) in the carbonate minerals is noticed on band shifts. Thus, electronic bands in the UV–Vis–NIR spectra and the overtones and combination bands of OH and carbonate ion in NIR show shifts to higher wavenumbers, particularly for widgiemoolthalite and takovite.

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Natural iowaite, magnesium–ferric oxychloride mineral having light green color originating from Australia has been characterized by EPR, optical, IR, and Raman spectroscopy. The optical spectrum exhibits a number of electronic bands due to both Fe(III) and Mn(II) ions in iowaite. From EPR studies, the g values are calculated for Fe(III) and g and A values for Mn(II). EPR and optical absorption studies confirm that Fe(III) and Mn(II) are in distorted octahedral geometry. The bands that appear both in NIR and Raman spectra are due to the overtones and combinations of water and carbonate molecules. Thus EPR, optical, and Raman spectroscopy have proven most useful for the study of the chemistry of natural iowaite and chemical changes in the mineral.

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Specialised support for student nurses making the transition to graduate nurse can be crucial to successful and smooth adjustment, and can create a path to positive and stable career experiences. This paper describes an enhanced model of final year nursing student placements which was trialled in 2006 at the Queensland University of Technology. The model involved collaboration with two major urban health services and resources were developed to support effective transition experiences. Ninety-two students, including 29 trial participants and 63 non-trial participants were assessed on preparedness for professional practice, before and after the trial semester. Results indicated an increase in preparedness across the entire sample, but students participating in the trial did not differ significantly in overall preparedness change from those who did not participate. Higher baseline preparedness in the trial group highlighted the possibility that proactive students who choose enrichment experiences tend to be likelier to gain benefit from such options than those who do not. Qualitative findings from focus groups conducted with 12 transition group students highlighted that one of the main beneficial aspects of the experience for students was the sense of belonging to a team that understood their learning needs and could work constructively with them.