Tuning the valence of the cerium center in (Na)phthalocyaninato and porphyrinato cerium double-deckers by changing the nature of the tetrapyrrole ligands

A series of 7 cerium double-decker complexes with various tetrapyrrole ligands including porphyrinates, phthalocyaninates, and 2,3-naphthalocyaninates have been prepared by previously described methodologies and characterized with elemental analysis and a range of spectroscopic methods. The molecular structures of two heteroleptic \[(na)phthalocyaninato](porphyrinato) complexes have also been determined by X-ray diffraction analysis which exhibit a slightly distorted square antiprismatic geometry with two domed ligands. Having a range of tetrapyrrole ligands with very different electronic properties, these compounds have been systematically investigated for the effects of ligands on the valence of the cerium center. On the basis of the spectroscopic (UV−vis, near-IR, IR, and Raman), electrochemical, and structural data of these compounds and compared with those of the other rare earth(III) counterparts reported earlier, it has been found that the cerium center adopts an intermediate valence in these complexes. It assumes a virtually trivalent state in cerium bis(tetra-tert-butylnaphthalocyaninate) as a result of the two electron rich naphthalocyaninato ligands, which facilitate the delocalization of electron from the ligands to the metal center. For the rest of the cerium double-deckers, the cerium center is predominantly tetravalent. The valences (3.59−3.68) have been quantified according to their LIII-edge X-ray absorption near-edge structure (XANES) profiles.

Tangible interfaces to explain Gaudi's use of ruled-surface geometries

This paper summarises the development of a machine-readable model series for explaining Gaudi's use of ruled surface geometry in the Sagrada Familia in Barcelona, Spain. The first part discusses the modeling methods underlying the columns of the cathedral and the techniques required to translate them into built structures. The second part discusses the design and development of a tangible machine-readable model to explain column-modeling methods interactively in educational contexts such as art exhibitions. It is designed to explain the principles underlying the column design by means of physical interaction without using mathematical terms or language.

Improvements to the design of Litesteel Beams undergoing lateral distortional buckling

An Australian manufacturer has recently developed an innovative group of cold-formed steel hollow flange sections, one of them is LiteSteel Beams (LSBs). The LSB sections are produced from thin and high strength steels by a patented manufacturing process involving simultaneous cold-forming and dual electric resistance welding. They have a unique geometry consisting of rectangular hollow flanges and a relatively slender web. The LSB flexural members are subjected to lateral distortional buckling effects and hence their capacities are reduced for intermediate spans. The current design rules for lateral distortional buckling were developed based on the lower bound of numerical and experimental results. The effect of LSB section geometry was not considered although it could influence the lateral distortional buckling performance. Therefore an accurate finite element model of LSB flexural members was developed and validated using experimental and finite strip analysis results. It was then used to investigate the effect of LSB geometry. The extensive moment capacity data thus developed was used to develop improved design rules for LSBs with one of them considering the LSB geometry effects through a modified slenderness parameter. The use of the new design rules gave higher lateral distortional buckling capacities for LSB sections with intermediate slenderness. The new design rule is also able to accurately predict the lateral distortional buckling moment capacities of other hollow flange beams (HFBs).

Tris[4,4,4-trifluoro-1-(2-thienyl)butane-1,3-dionato]aluminium(III)-tris[4,4,4-trifluoro-1-(2-thienyl)butane-1,3-dionato]iron(III) (3/1)

In the title compound, [Al(C8H4F3O2S)3]3[Fe(C8H4F3O2S)3], the metal centre is statistically occupied by AlIII and FeIII cations in a 3:1 ratio. The metal centre is within an octahedral O6 donor set defined by three chelating substituted acetoacetonate anions. The ligands are arranged around the periphery of the molecule with a mer geometry of the S atoms.

Modelling ideal turbulent vortex breakdown

In this computational study we investigate the role of turbulence in ideal axisymmetric vortex breakdown. A pipe geometry with a slight constriction near the inlet is used to stabilise the location of the breakdown within the computed domain. Eddy-viscosity and differential Reynolds stress models are used to model the turbulence. Changes in upstream turbulence levels, flow Reynolds and Swirl numbers are considered. The different computed solutions are monitored for indications of different breakdown flow configurations. Trends in vortex breakdown due to turbulent flow conditions are identified and discussed.

Application of bag sampling technique for particle size distribution measurements

Bag sampling techniques can be used to temporarily store an aerosol and therefore provide sufficient time to utilize sensitive but slow instrumental techniques for recording detailed particle size distributions. Laboratory based assessment of the method were conducted to examine size dependant deposition loss coefficients for aerosols held in VelostatTM bags conforming to a horizontal cylindrical geometry. Deposition losses of NaCl particles in the range of 10 nm to 160 nm were analysed in relation to the bag size, storage time, and sampling flow rate. Results of this study suggest that the bag sampling method is most useful for moderately short sampling periods of about 5 minutes.

Effect of orthokeratology on peripheral aberrations of the eye

Purpose: To investigate the effect of orthokeratology on peripheral aberrations in two myopic volunteers. Methods: The subjects wore reverse geometry orthokeratology lenses overnight and were monitored for 2 weeks of wear. They underwent corneal topography, peripheral refraction (out to ±34° along the horizontal visual field) and peripheral aberration measurements across the 42° × 32° central visual field using a modified Hartmann-Shack aberrometer. Results: Spherical equivalent refraction was corrected for the central 25° of the visual fields beyond which it gradually returned to its preorthokeratology values. There were increases in axial coma, spherical aberration, higher order root mean square aberrations, and total root-mean-squared aberrations (excluding defocus). The rates of change of vertical and horizontal coma across the field changed in sign. Total root mean square aberrations showed a quadratic rate of change across the visual field which was greater subsequent to orthokeratology. Conclusion: Although orthokeratology can correct peripheral relative hypermetropia it induces dramatic increases in higher-order aberrations across the field

Dynamics of railway wagons subjected to braking/traction torque

Braking or traction torque is regarded as an important source of wheelset skid and a potential source of derailment risk that adversely affects the safety levels of train operations; therefore, this research examines the effect of braking/traction torque to the longitudinal and lateral dynamics of wagons. This paper reports how train operations safety could be adversely affected due to various braking strategies. Sensitivity of wagon dynamics to braking severity is illustrated through numerical examples. The influence of wheel/rail interface friction coefficient and the effects of two types of track geometry defects on wheel unloading ratio and wagon pitch are also discussed in the paper.

Corrosion studies on the plasma-sprayed nanostructured titanium dioxide coating

Purpose: The purpose of this paper is to report the resistance of plasma-sprayed titanium dioxide (TiO2) nanostructured coatings in a corrosive environment.----- Design/methodology/approach: Weight loss studies are performed according to ASTM G31 specifications in 3.5?wt% NaCl. Electrochemical polarization resistance measurements are made according to ASTM G59-91 specifications. Corrosion resistance in a humid and corrosive environment is determined by exposing the samples in a salt spray chamber for 100?h. Microstructural studies are carried out using an atomic force microscope and scanning electron microscope.----- Findings: The nanostructured TiO2 coatings offer good resistance to corrosion, as shown by the results of immersion, electrochemical and salt spray studies. The corrosion resistance of the coating is dictated primarily by the geometry of splat lamellae, density of unmelted nanoparticles, magnitude of porosity and surface homogeneity.----- Practical implications: The TiO2 nanostructured coatings show promising potential for use as abrasion, wear-resistant and thermal barrier coatings for service in harsh environments.----- Originality/value: The paper relates the corrosion resistance of nanostructured TiO2 coatings to their structure and surface morphology.

Microphone array shape calibration in diffuse noise fields

This correspondence presents a microphone array shape calibration procedure for diffuse noise environments. The procedure estimates intermicrophone distances by fitting the measured noise coherence with its theoretical model and then estimates the array geometry using classical multidimensional scaling. The technique is validated on noise recordings from two office environments.

An application of near-infrared and mid-infrared spectroscopy to the study of selected minerals

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.

An old language for a new landscape

Because aesthetics can have a profound effect upon the human relationship to the non-human environment the importance of aesthetics to ecologically sustainable designed landscapes has been acknowledged. However, in recognition that the physical forms of designed landscapes are an expression of the social values of the time, some design professionals have called for a new aesthetic ― one that reflects these current ecological concerns. To address this, some authors have suggested various theoretical design frameworks upon which such an aesthetic could be based. Within these frameworks there is an underlying theme that the patterns and processes of natural systems have the potential to form a new aesthetic for landscape design —an aesthetic based on fractal rather than Euclidean geometry. Perry, Reeves and Sim (2008) have shown that it is possible to differentiate between different landscape forms by fractal analysis. However, this research also shows that individual scenes from within very different landscape forms can possess the same fractal properties. Early data, revealed by transforming landscape images from the spatial to the frequency domain, using the fast Fourier transform, suggest that fractal patterning can have a significant effect within the landscape. In fact, it may be argued that any landscape design that includes living processes will include some design element whose ultimate form can only be expressed through the mathematics of fractal geometry. This paper will present ongoing research into the potential role of fractal geometry as a basis for a new form language – a language that may articulate an aesthetic for landscape design that echoes our ecological awakening.

Optical absorption, infrared, Raman and EPR spectral studies on natural Iowaite mineral

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.

Three Carrier Ambiguity Resolutions : Generalised problems, models and solutions

In this paper, the problems of three carrier phase ambiguity resolution (TCAR) and position estimation (PE) are generalized as real time GNSS data processing problems for a continuously observing network on large scale. In order to describe these problems, a general linear equation system is presented to uniform various geometry-free, geometry-based and geometry-constrained TCAR models, along with state transition questions between observation times. With this general formulation, generalized TCAR solutions are given to cover different real time GNSS data processing scenarios, and various simplified integer solutions, such as geometry-free rounding and geometry-based LAMBDA solutions with single and multiple-epoch measurements. In fact, various ambiguity resolution (AR) solutions differ in the floating ambiguity estimation and integer ambiguity search processes, but their theoretical equivalence remains under the same observational systems models and statistical assumptions. TCAR performance benefits as outlined from the data analyses in some recent literatures are reviewed, showing profound implications for the future GNSS development from both technology and application perspectives.

Impact and energy absorption of empty and foam-filled conical tubes

Foam-filled conical tubes have recently emerged as efficient energy absorbing devices to mitigate the adverse effects of impacts. The primary aim of this thesis was to generate research and design information on the impact and energy absorption response of empty and foam-filled conical tubes, and to facilitate their application in energy absorbing systems under axial and oblique loading conditions representative of those typically encountered in crashworthiness and impact applications. Finite element techniques supported by experiments and existing results were used in the investigation. Major findings show that the energy absorption response can be effectively controlled by varying geometry and material parameters. A useful empirical formula was developed for providing engineering designers with an initial estimate of the load ratio and hence energy absorption performances of these devices. It was evident that foam-filled conical tubes enhance the energy absorption capacity and stabilise the crush response for both axial and oblique impact loading without a significant increase in the initial peak load. This is practically beneficial when higher kinetic energy needs to be absorbed, thus reducing the impact force transmitted to the protected structure and occupants. Such tubes also increase and maintain the energy absorption capacity under global bending as well as minimise the reduction of energy absorption capacity with increasing load angle. Furthermore, the results also highlight the feasibility of adding a foam-filled conical tube as a supplementary device in energy absorbing systems, since the overall energy absorption performance of such systems can be favourably enhanced by only including a relatively small energy absorbing device. Above all, the results demonstrate the superior performance of foam-filled conical tube for mitigating impact energy in impact and crashworthiness applications.