Mixed saturated-unsaturated alkyl-chain assemblies: Solid solutions of zinc stearate and zinc oleate

The linear saturated stearic acid and the bent mono-unsaturated oleic acid do not mix and form solid solutions. However, the zinc salts of these acids can. From X-ray diffraction and DSC measurements we show that the layered zinc stearate and zinc oleate salts form a homogeneous solid solution at all composition ratios. The solid solutions exhibit a single melting endotherm, with the melting temperature varying linearly with composition but with the enthalpy change showing a minimum. By monitoring features in the infrared spectra that are characteristic of the global conformation of the hydrocarbon chain, and hence can distinguish between stearate and oleate chains, it is shown that solid solution formation is realized by the introduction of gauche defects in a fraction of the stearate chains that are then no longer linear. This fraction increases with oleate concentration. It has also been possible from the spectroscopic measurements to establish a quantitative relation between molecular conformational order and the thermodynamic enthalpy of melting of the solid solutions.

Mixed pixel analysis for flood mapping using extended support vector machine

This paper addresses the challenges of flood mapping using multispectral images. Quantitative flood mapping is critical for flood damage assessment and management. Remote sensing images obtained from various satellite or airborne sensors provide valuable data for this application, from which the information on the extent of flood can be extracted. However the great challenge involved in the data interpretation is to achieve more reliable flood extent mapping including both the fully inundated areas and the 'wet' areas where trees and houses are partly covered by water. This is a typical combined pure pixel and mixed pixel problem. In this paper, an extended Support Vector Machines method for spectral unmixing developed recently has been applied to generate an integrated map showing both pure pixels (fully inundated areas) and mixed pixels (trees and houses partly covered by water). The outputs were compared with the conventional mean based linear spectral mixture model, and better performance was demonstrated with a subset of Landsat ETM+ data recorded at the Daly River Basin, NT, Australia, on 3rd March, 2008, after a flood event.

Mixed pixel analysis and assessment for flood mapping

The most difficult operation in flood inundation mapping using optical flood images is to map the ‘wet’ areas where trees and houses are partly covered by water. This can be referred to as a typical problem of the presence of mixed pixels in the images. A number of automatic information extracting image classification algorithms have been developed over the years for flood mapping using optical remote sensing images, with most labelling a pixel as a particular class. However, they often fail to generate reliable flood inundation mapping because of the presence of mixed pixels in the images. To solve this problem, spectral unmixing methods have been developed. In this thesis, methods for selecting endmembers and the method to model the primary classes for unmixing, the two most important issues in spectral unmixing, are investigated. We conduct comparative studies of three typical spectral unmixing algorithms, Partial Constrained Linear Spectral unmixing, Multiple Endmember Selection Mixture Analysis and spectral unmixing using the Extended Support Vector Machine method. They are analysed and assessed by error analysis in flood mapping using MODIS, Landsat and World View-2 images. The Conventional Root Mean Square Error Assessment is applied to obtain errors for estimated fractions of each primary class. Moreover, a newly developed Fuzzy Error Matrix is used to obtain a clear picture of error distributions at the pixel level. This thesis shows that the Extended Support Vector Machine method is able to provide a more reliable estimation of fractional abundances and allows the use of a complete set of training samples to model a defined pure class. Furthermore, it can be applied to analysis of both pure and mixed pixels to provide integrated hard-soft classification results. Our research also identifies and explores a serious drawback in relation to endmember selections in current spectral unmixing methods which apply fixed sets of endmember classes or pure classes for mixture analysis of every pixel in an entire image. However, as it is not accurate to assume that every pixel in an image must contain all endmember classes, these methods usually cause an over-estimation of the fractional abundances in a particular pixel. In this thesis, a subset of adaptive endmembers in every pixel is derived using the proposed methods to form an endmember index matrix. The experimental results show that using the pixel-dependent endmembers in unmixing significantly improves performance.

Unsteady mixed convection on the stagnation-point flow adjacent to a vertical plate with a magnetic field

An analysis is performed to study the unsteady combined forced and free convection flow (mixed convection flow) of a viscous incompressible electrically conducting fluid in the vicinity of an axisymmetric stagnation point adjacent to a heated vertical surface. The unsteadiness in the flow and temperature fields is due to the free stream velocity, which varies arbitrarily with time. Both constant wall temperature and constant heat flux conditions are considered in this analysis. By using suitable transformations, the Navier-Stokes and energy equations with four independent variables (x, y, z, t) are reduced to a system of partial differential equations with two independent variables (eta, tau). These transformations also uncouple the momentum and energy equations resulting in a primary axisymmetric flow, in an energy equation dependent on the primary flow and in a buoyancy-induced secondary flow dependent on both primary flow and energy. The resulting system of partial differential equations has been solved numerically by using both implicit finite-difference scheme and differential-difference method. An interesting result is that for a decelerating free stream velocity, flow reversal occurs in the primary flow after certain instant of time and the magnetic field delays or prevents the flow reversal. The surface heat transfer and the surface shear stress in the primary flow increase with the magnetic field, but the surface shear stress in the buoyancy-induced secondary flow decreases. Further the heat transfer increases with the Prandtl number, but the surface shear stress in the secondary flow decreases.

Use of the liquid-liquid interface for generating ultrathin nanocrystalline films of metals, chalcogenides, and oxides

The air-water interface has traditionally been employed to prepare particle assemblies and films of metals and semiconductors. The interface between water and an organic liquid, however, has not been investigated sufficiently for possible use in preparing nanocrystals and thin films of materials. In this article, we demonstrate the use of the liquid-liquid interface as a medium for preparing ultrathin films of metals, chalcogenides and oxides. The method involves the reaction at the interface between a metal-organic compound in the organic layer and an appropriate reagent for reduction, sulfidation, etc. in the aqueous layer. Some of the materials discussed are nanocrystalline films of gold, CuS, CuSe, CuO, and Cu(OH)(2) formed at the liquid-liquid interface. The results reported in this article should demonstrate the versatility and potential of the liquid-liquid interface for preparing nanomaterials and ultrathin films and encourage further research in this area. (c) 2005 Elsevier Inc. All rights reserved.

Study of (Ba3MMWO9)-M-II-W-IV (M-II = Ca, Zn; M-IV = Ti, Zr) perovskite oxides: Competition between 3C and 6H perovskite structures

We describe an investigation of (Ba3MMWO9)-M-II-W-IV oxides for M-II = Ca, Zn, and other divalent metals and M-IV = Ti, Zr. In general, a 1:2-ordered 6H (hexagonal, P6(3)/mmc) perovskite structure is stabilized at high temperatures (1300 degrees C) for all of the (Ba3MTiWO9)-Ti-II oxides investigated. An intermediate phase possessing a partially ordered 1:1 double perovskite (3C) structure with the cation distribution, Ba-2(Zn2/3Ti1/3)(W2/3Ti1/3)O-6, is obtained at 1200 degrees C for Ba3ZnTiWO9. Sr substitution for Ba in the latter stabilizes the cubic 3C structure instead of the 6H structure. A metastable Ba3CaZrWO9 that adopts the 3C (cubic, Fm (3) over barm) structure has also been synthesized by a low-temperature metathesis route. Besides yielding several new perovskite oxides that may be useful as dielectric ceramics, the present investigation provides new insights into the complex interplay of crystal chemistry (tolerance factor) and chemical bonding (anion polarization and d(0)-induced distortion of metal-oxygen octahedra) in the stabilization of 6H versus 3C perovskite structures for the (Ba3MMWO9)-M-II-W-IV series.

Use of the liquid-liquid interface for generating ultrathin nanocrystalline films of metals,chalcogenides,and oxides

The air-water interface has traditionally been employed to prepare particle assemblies and films of metals and semiconductors. The interface between water and an organic liquid, however, has not been investigated sufficiently for possible use in preparing nanocrystals and thin films of materials. In this article, we demonstrate the use of the liquid-liquid interface as a medium for preparing ultrathin films of metals, chalcogenides and oxides. The method involves the reaction at the interface between a metal-organic compound in the organic layer and an appropriate reagent for reduction, sulfidation, etc. in the aqueous layer. Some of the materials discussed are nanocrystalline films of gold, CuS, CuSe, CuO, and Cu(OH)(2) formed at the liquid-liquid interface. The results reported in this article should demonstrate the versatility and potential of the liquid-liquid interface for preparing nanomaterials and ultrathin films and encourage further research in this area.

Family of Mixed-Valence Oxovanadium(IV/V) Dinuclear Entities Incorporating N4O3-Coordinating Heptadentate Ligands: Synthesis, Structure, and EPR Spectra

Dinuclear ((VVV)-V-IV) oxophenoxovanadates of general formula [V2O3L] have been synthesized in excellent yields by reacting bis(acetylacetonato)oxovanadium(IV) with H3L in a 2:1 ratio in acetone under an N-2 atmosphere. Here L3- is the deprotonated form of 2,6-bis[{{(2-hydroxybenzyl)(N',N'-(dimethylamino)ethyl)}amino}methyl]-4-methylphenol (H3L1), 2,6-bis[{{(5-methyl-2-hydroxybenzyl)(N',N'-(dimethylamino)ethyl)}amino}methyl]-4-methylphenol (H3L2) 2,6-bis[ {{(5-tert-butyl-2-hydroxybenzyl)(N',N'-(dimethylamino)ethyl)}amino}methyl]-4-methylphenoI (H3L3), 2,6-bis[{{(5-chloro-2-hydroxybenzyl)(N',N'-(dimethylamino)ethyl)}amino}methyl]-4-methylphenol (H3L4) , 2,6-bis[{{(5-bromo-2-hydroxybenzyl)(N',N'-(dimethylamino)ethyl)}amino}methyl]-4-methylphenol (H3L5), or 2,6-bis[{{(5-methoxy-2-hydroxybenzyl)(N',N'-(dimethylamino)ethyl)}amino}methyl]-4-methylphenol (H3L6). In [V2O3L1], both the metal atoms have distorted octahedral geometry. The relative disposition of two terminal V=O groups in the complex is essentially cis. The O=V...V=O torsion angle is 24.6(2)degrees. The V-O-oxo-V and V-O-phenoxo-V angles are 117.5(4) and 93.4(3)degrees, respectively. The V...V bond distance is 3.173(5) Angstrom. X-ray crystallography, IR, UV-vis, and H-1 and V-51 NMR measurements show that the mixed-valence complexes contain two indistinguishable vanadium atoms (type 111). The thermal ellipsoids of O2, O4, C10, C14, and C15 also suggests a type III complex in the solid state. EPR spectra of solid complexes at 77 K display a single line indicating the localization of the odd electron (3d(xy)(1)). Valence localization at 77 K is also consistent with the V-51 hyperfine structure of the axial EPR spectra (3d(xy)(1) ground state) of the complexes in frozen (77 K) dichloromethane solution: S = 1/2, g(parallel to) similar to 1.94, g(perpendicular to) similar to 1.98, A(parallel to) similar to 166 x 10(-4) cm(-1), and A(perpendicular to) similar to 68 x 10(-4) cm(-1). In contrast isotropic room-temperature solution spectra of the family have 15 hyperfine lines (g(iso) similar to 1.974 and A(iso) similar to 50 x 10(-4) cm(-1)) revealing that the unpaired electron is delocalized between the metal centers. Crystal data for the [V2O3L1].CH2Cl2 complex are as follows: chemical formula, C32H43O6N4C12V2; crystal system, monoclinic; space group, C2/c; a = 18.461(4), b = 17.230(3), c = 13.700(3) Angstrom; beta = 117.88(3)degrees; Z = 8.

Composition of aqueous solutions in equilibrium with sulfides and oxides of iron at 3500°C

Solutions of potassium chloride (pH-buffered and 1-molat) equilibrated at 350°C with pyrrhotite, pyrite, and magnetite contained approximately 1 millimole of reduced sulfur and less than 0.1 millimole of oxidized sulfur per kilogram. Similar solutions equilibrated with pyrite, magnetite, and hematite contained approximately 1 millimole of reduced sulfur, but 3 to 6 millimoles of oxidized sulfur per kilogram. Both types of solutions contained less than 0.1 millimole of iron per kilogram at pH ≥ 6 and approximately 100 millimoles per kilogram at pH 2.

Unusual dielectric response in B-site size-disordered hexagonal transition metal oxides

We discover that hexagonal holmium copper titanate (Ho2CuTiO6), has a unique and highly desirable combination of high dielectric constant, low losses, very small temperature coefficient, and low frequency dependence. Our first-principles calculations indicate that these exceptional properties result from a size-difference at the Cu/Ti B-site that suppresses the expected ferroelectric transition, combined with the dominance of intermediate-frequency polar vibrational modes in the dielectric response. Our results suggest that the use of such B-site disorder in alloys of hexagonal transition-metal oxides should generally result in similar robust dielectrics.

A novel sheet 4f-3d mixed-metal pyridine dicarboxylate: synthesis, structure, photophysical properties and its transformation to a perovskite oxide

The synthesis, characterization and photophysical properties of a 4f-3d mixed metal compound, Gd(H2O)(3)Co[C5N1H3-(COO)(2)](3), are described; the structure is unique, consisting of sheets with large pores ( ca. 7 angstrom diameter) in the sheets and transforms to a perovskite oxide at moderate temperatures.

Solvolytic disproportionation of non-stoichiometric oxides of praseodymium and terbiumstar, open

The solvolytic disproportionation of non-stoichiometric PrOχ and TbOχ in acid solutions to produce higher oxides has been investigated. Some new non-stoichiometric phases have been reported. A number of interesting features of the non-stoichiometric rare earth oxides have been discussed and the need for a satisfactory structural model has been pointed out.

Spectrophotometric and potentiometric investigations of copper (II)-ethanolamine complexes - Part II. Monoethanolamine (Analysis of mixed hydroxy complexes with polarographic evidence)

Potentiometric, spectrophotometric and polarographic evidence has been presented for the formation of mixed hydroxy complexes in coppermonoethanolamine system. A method has been developed for the analysis of Bjerrum formation curves taken in presence of 0·1, 0·2, 0·5 and 1·0 M monoethanolammonium ion with respect to hydroxy complexes. The formation of CuAOH+, CuA2OH+ and CuA3OH+ is shown and the corresponding stability constants are calculated at different concentrations of MEA ion. Curves showing the distribution of pure and hydroxy complexes at various pA values in solutions containing different concentrations of MEA ion have also been given.

Intraseasonal response of mixed layer temperature and salinity in the Bay of Bengal to heat and freshwater flux

Buoy and satellite data show pronounced subseasonal oscillations of sea surface temperature (SST) in the summertime Bay of Bengal. The SST oscillations are forced mainly by surface heat flux associated with the active break cycle of the south Asian summer monsoon. The input of freshwater (FW) from summer rain and rivers to the bay is large, but not much is known about subseasonal salinity variability. We use 2002-2007 observations from three Argo floats with 5 day repeat cycle to study the subseasonal response of temperature and salinity to surface heat and freshwater flux in the central Bay of Bengal. About 95% of Argo profiles show a shallow halocline, with substantial variability of mixed layer salinity. Estimates of surface heat and freshwater flux are based on daily satellite data sampled along the float trajectory. We find that intraseasonal variability of mixed layer temperature is mainly a response to net surface heat flux minus penetrative radiation during the summer monsoon season. In winter and spring, however, temperature variability appears to be mainly due to lateral advection rather than local heat flux. Variability of mixed layer freshwater content is generally independent of local surface flux (precipitation minus evaporation) in all seasons. There are occasions when intense monsoon rainfall leads to local freshening, but these are rare. Large fluctuations in FW appear to be due to advection, suggesting that freshwater from rivers and rain moves in eddies or filaments.

Shrewd alliances: mixed foraging associations between treeshrews,greater racket-tailed drongos and sparrowhawks on Great Nicobar Island, India

Mixed-species foraging associations may form to enhance feeding success or to avoid predators. We report the costs and consequences of an unusual foraging association between an endemic foliage gleaning tupaid (Nicobar treeshrew Tupaia nicobarica) and two species of birds; one an insectivorous commensal (greater racket-tailed drongo Dicrurus paradiseus) and the other a diurnal raptor and potential predator (Accipiter sp.). In an alliance driven, and perhaps engineered, by drongos, these species formed cohesive groups with predictable relationships. Treeshrew breeding pairs were found more frequently than solitary individuals with sparrowhawks and were more likely to tolerate sparrowhawks in the presence of drongos. Treeshrews maintained greater distances from sparrowhawks than drongos, and permitted the raptors to come closer when drongos were present. Treeshrew foraging rates declined in the presence of drongos; however, the latter may provide them predator avoidance benefits. The choice of the raptor to join the association is intriguing; particular environmental resource states may drive the evolution of such behavioural strategies. Although foraging benefits seem to be the primary driver of this association, predator avoidance also influences interactions, suggesting that strategies driving the formation of flocks may be complex and context dependent with varying benefits for different actors.