Characterization of Alloy-Spinel-Corundum Equilibrium in the System Fe-Ni-Al-O

The three phase equilibrium between alloy, spinel solid solution and α-alumina in the Fe-Ni-Al-O system has been fully characterized at 1823K as a function of alloy composition using both experimental and computational methods. The oxygen potential was measured using a solid state cell incorporating yttria-doped thoria as the electrolyte and Cr+ Cr2O3 as the reference electrode. Oxygen concentration of the alloy was determined by an inert gas fusion technique. The composition of the spinel solid solution, formed at the interface between the alloy and an alumina crucible, was determined by EPMA. The variation of the oxygen concentration and potential and composition of the spinel solid solution with mole fraction of nickel in the alloy have been computed using activities in binary Fe-Ni system, free energies of formation of end member spinels FeO•(1+x)Al2O3 and NiO•(1+x)Al2O3 and free energies of solution of oxygen in liquid iron and nickel, available in the literature. Activities in the spinel solid solution were computed using a cation distribution model. The variation of the activity coefficient of oxygen with alloy composition in Fe-Ni-O system was calculated using both the quasichemical model of Jacob and Alcock and the Wagner's model, with the correlation of Chiang and Chang. The computed results for the oxygen potential and the composition of the spinel solid solution are in good agreement with the measurements. The measured oxygen concentration lies between the values computed using models of Wagner and Jacob and Alcock. The results of the study indicate that the deoxidation hyper-surface in multicomponent systems can be computed with useful accuracy using data for end member systems and thermodynamic models.

Root system traits of Norway spruce, Scots pine, and silver birch in mixed boreal forests: an analysis of root architecture, morphology, and anatomy

The aim of this thesis was to unravel the functional-structural characteristics of root systems of Betula pendula Roth., Picea abies (L.) Karst., and Pinus sylvestris L. in mixed boreal forest stands differing in their developmental stage and site fertility. The root systems of these species had similar structural regularities: horizontally-oriented shallow roots defined the horizontal area of influence, and within this area, each species placed fine roots in the uppermost soil layers, while sinker roots defined the maximum rooting depth. Large radial spread and high ramification of coarse roots, and the high specific root length (SRL) and root length density (RLD) of fine roots indicated the high belowground competitiveness and root plasticity of B. pendula. Smaller radial root spread and sparser branching of coarse roots, and low SRL and RLD of fine roots of the conifers could indicate their more conservative resource use and high association with and dependence on ectomycorrhiza-forming fungi. The vertical fine root distributions of the species were mostly overlapping, implying the possibility for intense belowground competition for nutrients. In each species, conduits tapered and their frequency increased from distal roots to the stem, from the stem to the branches, and to leaf petioles in B. pendula. Conduit tapering was organ-specific in each species violating the assumptions of the general vascular scaling model (WBE). This reflects the hierarchical organization of a tree and differences between organs in the relative importance of transport, safety, and mechanical demands. The applied root model was capable of depicting the mass, length and spread of coarse roots of B. pendula and P. abies, and to the lesser extent in P. sylvestris. The roots did not follow self-similar fractal branching, because the parameter values varied within the root systems. Model parameters indicate differences in rooting behavior, and therefore different ecophysiological adaptations between species.

Antarctic ice shelf melting and its impact on the global sea ice-ocean system

Earth s ice shelves are mainly located in Antarctica. They cover about 44% of the Antarctic coastline and are a salient feature of the continent. Antarctic ice shelf melting (AISM) removes heat from and inputs freshwater into the adjacent Southern Ocean. Although playing an important role in the global climate, AISM is one of the most important components currently absent in the IPCC climate model. In this study, AISM is introduced into a global sea ice-ocean climate model ORCA2-LIM, following the approach of Beckmann and Goosse (2003; BG03) for the thermodynamic interaction between the ice shelf and ocean. This forms the model ORCA2-LIM-ISP (ISP: ice shelf parameterization), in which not only all the major Antarctic ice shelves but also a number of minor ice shelves are included. Using these two models, ORCA2-LIM and ORCA2-LIM-ISP, the impact of addition of AISM and increasing AISM have been investigated. Using the ORCA2-LIM model, numerical experiments are performed to investigate the sensitivity of the polar sea ice cover and the Antarctic Circumpolar Current (ACC) transport through Drake Passage (DP) to the variations of three sea ice parameters, namely the thickness of newly formed ice in leads (h0), the compressive strength of ice (P*), and the turning angle in the oceanic boundary layer beneath sea ice (θ). It is found that the magnitudes of h0 and P* have little impact on the seasonal sea ice extent, but lead to large changes in the seasonal sea ice volume. The variation in turning angle has little impact on the sea ice extent and volume in the Arctic but tends to reduce them in the Antarctica when ignored. The magnitude of P* has the least impact on the DP transport, while the other two parameters have much larger influences. Numerical results from ORCA2-LIM and ORCA2-LIM-ISP are analyzed to investigate how the inclusion of AISM affects the representation of the Southern Ocean hydrography. Comparisons with data from the World Ocean Circulation Experiment (WOCE) show that the addition of AISM significantly improves the simulated hydrography. It not only warms and freshens the originally too cold and too saline bottom water (AABW), but also warms and enriches the salinity of the originally too cold and too fresh warm deep water (WDW). Addition of AISM also improves the simulated stratification. The close agreement between the simulation with AISM and the observations suggests that the applied parameterization is an adequate way to include the effect of AISM in a global sea ice-ocean climate model. We also investigate the models capability to represent the sea ice-ocean system in the North Atlantic Ocean and the Arctic regions. Our study shows both models (with and without AISM) can successfully reproduce the main features of the sea ice-ocean system. However, both tend to overestimate the ice flux through the Nares Strait, produce a lower temperature and salinity in the Hudson Bay, Baffin Bay and Davis Strait, and miss the deep convection in the Labrador Sea. These deficiencies are mainly attributed to the artificial enlargement of the Nares Strait in the model. In this study, the impact of increasing AISM on the global sea ice-ocean system is thoroughly investigated. This provides a first idea regarding changes induced by increasing AISM. It is shown that the impact of increasing AISM is global and most significant in the Southern Ocean. There, increasing AISM tends to freshen the surface water, to warm the intermediate and deep waters, and to freshen and warm the bottom water. In addition, increasing AISM also leads to changes in the mixed layer depths (MLD) in the deep convection sites in the Southern Ocean, deepening in the Antarctic continental shelf while shoaling in the ACC region. Furthermore, increasing AISM influences the current system in the Southern Ocean. It tends to weaken the ACC, and strengthen the Antarctic coastal current (ACoC) as well as the Weddell Gyre and the Ross Gyre. In addition to the ocean system, increasing AISM also has a notable impact on the Antarctic sea ice cover. Due to the cooling of seawater, sea ice concentration and thickness generally become higher. In austral winter, noticeable increases in sea ice concentration mainly take place near the ice edge. In regards with sea ice thickness, large increases are mainly found along the coast of the Weddell Sea, the Bellingshausen and Amundsen Seas, and the Ross Sea. The overall thickening of sea ice leads to a larger volume of sea ice in Antarctica. In the North Atlantic, increasing AISM leads to remarkable changes in temperature, salinity and density. The water generally becomes warmer, more saline and denser. The most significant warming occurs in the subsurface layer. In contrast, the maximum salinity increase is found at the surface. In addition, the MLD becomes larger along the Greenland-Scotland-Iceland ridge. Global teleconnections due to AISM are studied. The AISM signal is transported with the surface current: the additional freshwater from AISM tends to enhance the northward spreading of the surface water. As a result, more warm and saline water is transported from the tropical region to the North Atlantic Ocean, resulting in warming and salt enrichment there. It would take about 30 40 years to establish a systematic noticeable change in temperature, salinity and MLD in the North Atlantic Ocean according to this study. The changes in hydrography due to increasing AISM are compared with observations. Consistency suggests that increasing AISM is highly likely a major contributor to the recent observed changes in the Southern Ocean. In addition, the AISM might contribute to the salinity contrast between the North Atlantic and North Pacific, which is important for the global thermohaline circulation.

Chemical potential of oxygen for iron-rutile-ilmenite and iron-ilmenite-ulvospinel equilibria

The chemical potential of oxygen corresponding to the iron-rutile-ilmenite (IRI) and iron-ilmenite-ulvospinel (IIU) equilibria has been measured employing solid-state galvanic cells,$$Pt, Fe + TiO_2 + FeTiO_3 //(Y_2 O_3 ) ZrO_2 //Fe + FeO, Pt$$ and $${\text{Pt, Fe + FeTiO}}_{\text{3}} {\text{ + Fe}}_{\text{2}} {\text{TiO}}_{\text{4}} {\text{//(Y}}_{\text{2}} {\text{0}}_{\text{3}} {\text{) ZrO}}_{\text{2}} {\text{//Fe + FeO, Pt}}$$ in the temperature range of 875 to 1275 K and 900 to 1373 K, respectively. The cells are written such that the right-hand electrodes are positive. The electromotive force (emf) of both the cells was found to be reversible and to vary linearly with temperature over the entire range of measurement. The chemical potential of oxygen for IRI equilibrium is represented by Δμo2(IRI) = -550,724 - 29.445T + 20.374T InT(±210) J mol−1 (875 <-T<- 1184 K) = -620,260 + 369.593T - 27.716T lnT(±210) J mol−1 (1184 <-T<- 1275 K) and that for IIU equilibrium by Δμo2(IIU) = -501,800 - 49.035T + 20.374T lnT(±210) J mol−1 (900 <-T<- 1184 K) = -571,336 + 350.003T− 27.716T lnT(=−210) J mol-1 (1184 <-T<- 1373 K) The standard Gibbs energy changes for IRI and IIU equilibria have been deduced from the measured oxygen potentials. Since ilmenite contains small amounts of Ti³+ ions, a correction for the activity of FeTiO3 has been incorporated by assuming ideal mixing on each cation sublattice in the FeTiO3-Ti2O3 system. Similarly, the ulvospinel contains some Fe³+ ions and a correction for the activity of Fe2TiO4 has been included by modeling the Fe2TiO4-Fe3O4 system. The third-law analysis of the results obtained for IRI equilibrium gives ΔH 298 0 = -575 (±1.0) kJ mol-1 and for IIU equilibrium yields ΔH 298 0 = -523.7 (±0.7) kJ mol−1}. The present results suggest that Fe2+ and Ti4+ cations mix almost ideally on the octahedral site of spinel lattice in Fe2TiO4, giving rise to a configurational contribution of 2R In 2 (11.5256 J mol-1 K-1) to the entropy of Fe2TiO4.

Literature Review: Investigating Drug Transport at the Blood-Brain Barrier and the Effects of P-glycoprotein on the Brain Distribution of Drugs.

The blood-brain barrier (BBB) is a unique barrier that strictly regulates the entry of endogenous substrates and xenobiotics into the brain. This is due to its tight junctions and the array of transporters and metabolic enzymes that are expressed. The determination of brain concentrations in vivo is difficult, laborious and expensive which means that there is interest in developing predictive tools of brain distribution. Predicting brain concentrations is important even in early drug development to ensure efficacy of central nervous system (CNS) targeted drugs and safety of non-CNS drugs. The literature review covers the most common current in vitro, in vivo and in silico methods of studying transport into the brain, concentrating on transporter effects. The consequences of efflux mediated by p-glycoprotein, the most widely characterized transporter expressed at the BBB, is also discussed. The aim of the experimental study was to build a pharmacokinetic (PK) model to describe p-glycoprotein substrate drug concentrations in the brain using commonly measured in vivo parameters of brain distribution. The possibility of replacing in vivo parameter values with their in vitro counterparts was also studied. All data for the study was taken from the literature. A simple 2-compartment PK model was built using the Stella™ software. Brain concentrations of morphine, loperamide and quinidine were simulated and compared with published studies. Correlation of in vitro measured efflux ratio (ER) from different studies was evaluated in addition to studying correlation between in vitro and in vivo measured ER. A Stella™ model was also constructed to simulate an in vitro transcellular monolayer experiment, to study the sensitivity of measured ER to changes in passive permeability and Michaelis-Menten kinetic parameter values. Interspecies differences in rats and mice were investigated with regards to brain permeability and drug binding in brain tissue. Although the PK brain model was able to capture the concentration-time profiles for all 3 compounds in both brain and plasma and performed fairly well for morphine, for quinidine it underestimated and for loperamide it overestimated brain concentrations. Because the ratio of concentrations in brain and blood is dependent on the ER, it is suggested that the variable values cited for this parameter and its inaccuracy could be one explanation for the failure of predictions. Validation of the model with more compounds is needed to draw further conclusions. In vitro ER showed variable correlation between studies, indicating variability due to experimental factors such as test concentration, but overall differences were small. Good correlation between in vitro and in vivo ER at low concentrations supports the possibility of using of in vitro ER in the PK model. The in vitro simulation illustrated that in the simulation setting, efflux is significant only with low passive permeability, which highlights the fact that the cell model used to measure ER must have low enough paracellular permeability to correctly mimic the in vivo situation.

Fe-57 Mössbauer and Mo K-EXAFS Investigations of MoxFe3-xO4, an Interesting Mixed-Valent Oxide System

Ferrites of the formula MoxFe3-xO4, prepared by a soft-chemistry route, show mixed valence states of both iron and molybdenum cations. Mössbauer studies show that Fe2+ and Fe3+ ions are present on both the A and B sites, giving Fe an average oxidation state between 2+ and 3+. Molybdenum is present in the 3+ and the 4+ states on the B sites. The presence of Mo in the 3+ state has been established by determining the Mo3+-O distance (2.2 Å), for the first time, by Mo K-EXAFS. The mixed valence of Fe on both the A and B sites and of Mo on the B sites is responsible for the fast electron transfer between the cations. All the Mössbauer parameters including the line width show a marked change at a composition (x ? 0.3) above which the concentration of Fe2+A increases rapidly.

Thermodynamic Study of Mixed Anionic Solid Solutions Using Gradient Solid Electrolytes System K2CO3 - K2SO4

The thermodynamic properties of K2CO3 -KSO, solid solutions with hexagonal structure have been measured using a solid-state cell, incorporating a composite solid electrolyte with step-changes in composition. The cell with the configuration Pt, CO2' + O2' || K2CO3 | K2(CO3)x(SO4)1-x || CO2'' + O2'' + Pt X =1 X=X was investigated in the temperature range of 925 to 1165 K. The composite gradient solid electrolyte consisted of pure K2CO3 at one extremity and the solid solution under study at the other. The Nernstian response of the cell to changes in partial pressures of CO2 and O2 at the electrodes and temperature was demonstrated. The activity of K2CO3 in the solid solution was measured by three techniques. All three methods gave identical results, indicating unit transport number for K+ ions and negligible diffusion potential due to concentration gradients of carbonate and sulfate ions. The activity of K2CO3 exhibits positive deviation from Raoult's law. The excess Gibbs energy of mixing of the solid solution can be represented using a subregular solution model DELTAG(E) = X(1 - X)[5030X + 4715(1 - X)] J mol-1 By combining this information with the phase diagram, mixing properties of the liquid phase were obtained.

Phase-relations in the system CAO-SIO2-ZRO2 AT 1573-K

Zirconia-based solid electrolytes with zircon (ZrSiO4) as the auxiliary electrode have been suggested of sensing silicon concentrations in iron and steel melts. A knowledge of phase relations in the ternary system MO-SiO2-ZrO2 (M = Ca, Mg) is useful for selecting an appropriate auxiliary electrode. In this investigation, an isothermal section for the phase diagram of the system CaO-SiO2ZrO2 at 1573 K has been established by equilibrating mixtures of component oxides in air, followed by quenching and phase identification by optical miroscopy, energy disperse analysis of X-rays (EDAX) and X-ray diffraction analysis (XRD). The equilibrium phase relations have also been confirmed by computation using the available thermodynamic data on condensed phases in the system. The results indicate that zircon is not in thermodynamic equilibrium with calcia-stabilized zirconia or calcium zirconate. The silica containing phase in equilibrium with stabilized zirconia is Ca3ZrSi2O9. Calcium zirconate can coexist with Ca3ZrSi2O9 and Ca2SiO4.

Electrical transport properties of 0.5Li(2)O-0.5M(2)O-2B(2)O(3) (M = Li, Na and K) glasses

Transparent glasses in the system 0.5Li(2)O-0.5M(2)O-2B(2)O(3) (M = Li, Na and K) were fabricated via the conventional melt quenching technique. The amorphous and glassy nature of the samples was confirmed via the X-ray powder diffraction and the differential scanning calorimetry, respectively. The frequency and temperature dependent characteristics of the dielectric relaxation and the electrical conductivity were investigated in the 100 Hz-10 MHz frequency range. The imaginary part of the electric modulus spectra was modeled using an approximate solution of Kohrausch-Williams-Watts relation. The stretching exponent, (3, was found to be temperature independent for 0.5Li(2)O-0.5Na(2)O-2B(2)O(3) (LNBO) glasses. The activation energy associated with DC conduction was found to be higher (1.25 eV) for 0.5Li(2)O-0.5K(2)O-2B(2)O(3) (LKBO) glasses than that of the other glass systems under study. This is attributed to the mixed cation effect. (C) 2011 Elsevier By. All rights reserved.

Peristaltic transport of a biofluid in a pipe of elliptic cross section

Peristaltic transport of two fluids occupying the peripheral layer and the core in an elliptic tube is, investigated in elliptic cylindrical co-ordinate system, under long wavelength and low Reynolds number approximations. The effect of peripheral-layer viscosity on the flow rate and the frictional force for a slightly elliptic tube is discussed. The limiting results for the one-fluid model are obtained for different eccentricities of the undisturbed tube cross sections with the same area. As a result of non-uniformity of the peristaltic wave, two different amplitude ratios are defined and the time-averaged flux and mechanical efficiency are studied for different eccentricities. It is observed that the time-averaged flux is not affected significantly by the pressure drop when the eccentricity is large. For the peristaltic waves with same area variation, the pumping seems to improve with the eccentricity.

Lithium ion transport in Li2SO4-Li2O-B2O3 glasses

Electrical conductivity and dielectric relaxation studies with a wide range of compositions of lithium ion conducting glasses belonging to the ternary glass system Li2SO4-Li2O-B2-O3- have been carried out over the temperature range 150-450 K and between 10 - 10(7) Hz. DC conductivities exhibit two different activation regions. This seems to suggest the presence of a cluster tissue texture in these glasses with weakly ordered clusters of Li2SO4 and lithium berates being held together by a truly amorphous tissue of the same average composition as clusters. AC conductivity behaviour of these glasses has been analysed using both power law and stretched exponential relaxation functions. The variation of the power law exponent s and the stretched exponent beta with temperature seems to be consistent with the presence of a cluster tissue texture in these glasses.

Role of PbO in lithium ion transport in Li2O-PbO-B2O3 glasses

Abstract: A wide range of compositions of grasses in the ternary Li2O-PbO-B2O3 glass system was prepared, and de and ac conductivity measurements were carried out on these glasses. The presence of lead leads to a decrease in de conductivities and an increase in the activation energies. This is likely to be due to the increase of the partial charges on the oxygen atoms and to the presence of the lone pair on the Pb atom; both of these factors impede lithium ion motion. The ac conductivity and dielectric behavior of these glasses support such a conjecture. (C) 2000 Elsevier Science Ltd.

An organically templated iron sulfate with a distorted Kagome lattice exhibiting unusual magnetic properties

A layered iron sulfate of the composition [H3N(CH2)(2)NH2(CH2)(2)NH2(CH2)(2)NH3][(Fe3F6)-F-II(SO4)(2)], possessing a distorted Kagome lattice, prepared hydrothermally, is found to exhibit magnetic hysteresis like a ferrimagnet besides the characteristics of a frustrated system, like those of a spin glass.

A scaling analysis of momentum and heat transport in laser surface melting

In this paper, we outline a systematic procedure for scaling analysis of momentum and heat transfer in laser melted pools. With suitable choices of non-dimensionalising parameters, the governing equations coupled with appropriate boundary conditions are first scaled, and the relative significance of various terms appearing in them are accordingly analysed. The analysis is then utilised to predict the orders of magnitude of some important quantities, such as the velocity scale at the top surface, velocity boundary layer thickness, maximum temperature rise in the pool, fully developed pool-depth, and time required for initiation of melting. Using the scaling predictions, the influence of various processing parameters on the system variables can be well recognised, which enables us to develop a deeper insight into the physical problem of interest. Moreover, some of the quantities predicted from the scaling analysis can be utilised for optimised selection of appropriate grid-size and time-steps for full numerical simulation of the process. The scaling predictions are finally assessed by comparison with experimental and numerical results quoted in the literature, and an excellent qualitative agreement is observed.

Rule-based modelling of iron homeostasis in tuberculosis

To establish itself within the host system, Mycobacterium tuberculosis (Mtb) has formulated various means of attacking the host system. One such crucial strategy is the exploitation of the iron resources of the host system. Obtaining and maintaining the required concentration of iron becomes a matter of contest between the host and the pathogen, both trying to achieve this through complex molecular networks. The extent of complexity makes it important to obtain a systems perspective of the interplay between the host and the pathogen with respect to iron homeostasis. We have reconstructed a systems model comprising 92 components and 85 protein-protein or protein-metabolite interactions, which have been captured as a set of 194 rules. Apart from the interactions, these rules also account for protein synthesis and decay, RBC circulation and bacterial production and death rates. We have used a rule-based modelling approach, Kappa, to simulate the system separately under infection and non-infection conditions. Various perturbations including knock-outs and dual perturbation were also carried out to monitor the behavioral change of important proteins and metabolites. From this, key components as well as the required controlling factors in the model that are critical for maintaining iron homeostasis were identified. The model is able to re-establish the importance of iron-dependent regulator (ideR) in Mtb and transferrin (Tf) in the host. Perturbations, where iron storage is increased, appear to enhance nutritional immunity and the analysis indicates how they can be harmful for the host. Instead, decreasing the rate of iron uptake by Tf may prove to be helpful. Simulation and perturbation studies help in identifying Tf as a possible drug target. Regulating the mycobactin (myB) concentration was also identified as a possible strategy to control bacterial growth. The simulations thus provide significant insight into iron homeostasis and also for identifying possible drug targets for tuberculosis.