Long-range Coulomb interactions and nanoscale electronic inhomogeneities in correlated oxides

Electronic, magnetic, or structural inhomogeneities ranging in size from nanoscopic to mesoscopic scales seem endemic and are possibly generic to colossal magnetoresistance manganites and other transition metal oxides. They are hence of great current interest and understanding them is of fundamental importance. We show here that an extension, to include long-range Coulomb interactions, of a quantum two-fluid l-b model proposed recently for manganites [Phys. Rev. Lett. 92, 157203 (2004)] leads to an excellent description of such inhomogeneities. In the l-b model two very different kinds of electronic states, one localized and polaronic (l) and the other extended or broad band (b) coexist. For model parameters appropriate to manganites and even within a simple dynamical mean-field theory (DMFT) framework, it describes many of the unusual phenomena seen in manganites, including colossal magnetoresistance (CMR), qualitatively and quantitatively. However, in the absence of long-ranged Coulomb interaction, a system described by such a model would actually phase separate, into macroscopic regions of l and b electrons, respectively. As we show in this paper, in the presence of Coulomb interactions, the macroscopic phase separation gets suppressed and instead nanometer scale regions of polarons interspersed with band electron puddles appear, constituting a kind of quantum Coulomb glass. We characterize the size scales and distribution of the inhomogeneity using computer simulations. For realistic values of the long-range Coulomb interaction parameter V-0, our results for the thresholds for occupancy of the b states are in agreement with, and hence support, the earlier approach mentioned above based on a configuration averaged DMFT treatment which neglects V-0; but the present work has features that cannot be addressed in the DMFT framework. Our work points to an interplay of strong correlations, long-range Coulomb interaction, and dopant ion disorder, all inevitably present in transition metal oxides as the origin of nanoscale inhomogeneities rather than disorder frustrated phase competition as is generally believed. As regards manganites, it argues against explanations for CMR based on disorder frustrated phase separation and for an intrinsic origin of CMR. Based on this, we argue that the observed micrometer (meso) scale inhomogeneities owe their existence to extrinsic causes, e.g., strain due to cracks and defects. We suggest possible experiments to validate our speculation.

Role of cell attachment in leaching of chalcopyrite mineral by Thiobacillus ferrooxidans

Experiments on the leaching of copper from chalcopyrite mineral by the bacterium Thiobacillus ferrooxidans show that, in the presence of adequate amounts of sulphide, iron-grown bacteria preferentially oxidise sulphur in the ore (through direct attachment) rather than ferrous sulphate in solution. At 20% pulp density, the leaching initially takes place by a predominantly direct mechanism. The cell density in the liquid phase increases, but the Fe2+ is not oxidised. However, in the later stages when less solid substrate is available and the cell density becomes very high, the bacteria start oxidising Fe2+ in the liquid phase, thus contributing to the indirect mechanism of leaching. Contrary to expectations, the rate of leaching increased with increasing particle size in spite of the decreasing specific surface area. This has been found to be due to increasing attachment efficiency with increase in particle size.

Fabrication and mechanisms of densification of ZrB2-based ultra high temperature ceramics by reactive hot pressing

Dense ZrB2-SiC (25-30 vol%) composites have been produced by reactive hot pressing using stoichiometric Zr, B4C, C and Si powder mixtures with and without Ni addition at 40 MPa, 1600 degrees C for 60 min. Nickel, a common additive to promote densification, is shown not to be essential; the presence of an ultra-fine microstructure containing a transient plastic ZrC phase is suggested to play a key role at low temperatures, while a transient liquid phase may be responsible at temperatures above 1350 degrees C. Hot Pressing of non-stoichiometric mixture of Zr, B4C and Si at 40 MPa, 1600 degrees C for 30 min resulted in ZrB2-ZrCx-SiC (15 vol%) composites of similar to 98% RD.

Ferrous iron oxidation by foam immobilized Acidithiobacillus ferrooxidans: Experiments and modeling

Ferrous iron bio-oxidation by Acidithiobacillus ferrooxidans immobilized on polyurethane foam was investigated. Cells were immobilized on foams by placing them in a growth environment and fully bacterially activated polyurethane foams (BAPUFs) were prepared by serial subculturing in batches with partially bacterially activated foam (pBAPUFs). The dependence of foam density on cell immobilization process, the effect of pH and BAPUF loading on ferrous oxidation were studied to choose operating parameters for continuous operations. With an objective to have high cell densities both in foam and the liquid phase, pretreated foams of density 50 kg/m3 as cell support and ferrous oxidation at pH 1.5 to moderate the ferric precipitation were preferred. A novel basket-type bioreactor for continuous ferrous iron oxidation, which features a multiple effect of stirred tank in combination with recirculation, was designed and operated. The results were compared with that of a free cell and a sheet-type foam immobilized reactors. A fivefold increase in ferric iron productivity at 33.02 g/h/L of free volume in foam was achieved using basket-type bioreactor when compared to a free cell continuous system. A mathematical model for ferrous iron oxidation by Acidithiobacillus ferrooxidans cells immobilized on polyurethane foam was developed with cell growth in foam accounted by an effectiveness factor. The basic parameters of simulation were estimated using the experimental data on free cell growth as well as from cell attachment to foam under nongrowing conditions. The model predicted the phase of both oxidation of ferrous in shake flasks by pBAPUFs as well as by fully activated BAPUFs for different cell loadings in foam. Model for stirred tank basket bioreactor predicted within 5% both transient and steady state of the experiments closely for the simulated dilution rates. Bio-oxidation at high Fe2+ concentrations were simulated with experiments when substrate and product inhibition coefficients were factored into cell growth kinetics.

Multicarrier conduction and Boltzmann transport analysis of heavy hole mobility in HgCdTe near room temperature

Magnetotransport measurements in pulsed fields up to 15 T have been performed on mercury cadmium telluride (Hg1-xCdxTe, x similar to 0.2) bulk as well as liquid phase epitaxially grown samples to obtain the resistivity and conductivity tensors in the temperature range 220-300 K. Mobilities and densities of various carriers participating in conduction have been extracted using both conventional multicarrier fitting (MCF) and mobility spectrum analysis. The fits to experimental data, particularly at the highest magnetic fields, were substantially improved when MCF is applied to minimize errors simultaneously on both resistivity and conductivity tensors. The semiclassical Boltzmann transport equation has been solved without using adjustable parameters by incorporating the following scattering mechanisms to fit the mobility: ionized impurity, polar and nonpolar optical phonons, acoustic deformation potential, and alloy disorder. Compared to previous estimates based on the relaxation time approximation with outscattering only, polar optical scattering and ionized impurity scattering limited mobilities are shown to be larger due to the correct incorporation of the inscattering term taking into account the overlap integrals in the valence band.

Scanning Tunneling Spectroscopy on Pr0.68Pb0.32MnO3 single crystals

Scanning tunneling microscopy/spectroscopy studies were carried out on single crystals of colossal magnetoresistive manganite Pr0.68Pb0.32MnO3 at different temperatures in order to probe their spatial homogeneity across the metal-insulator transition temperature TM-I(similar to 255 K). A metallic behavior of the local conductance was observed for temperatures T < TM-I. Zero bias conductance (dI/dV)v=(0), which is directly proportional to the local surface density of states at the Fermi level, shows a single distribution at temperatures T < 200 K suggesting a homogeneous electronic phase at low temperatures. In a narrow temperature window of 200 K < T < TM-I, however, an inhomogeneous distribution of (dI/dV)v=(0) has been observed. This result gives evidence for phase separation in the transition region in this compound.

Scanning Tunneling Spectroscopy on Pr0.68Pb0.32MnO3 single crystals

Scanning tunneling microscopy/spectroscopy studies were carried out on single crystals of colossal magnetoresistive manganite Pr0.68Pb0.32MnO3 at different temperatures in order to probe their spatial homogeneity across the metal-insulator transition temperature TM-I(similar to 255 K). A metallic behavior of the local conductance was observed for temperatures T < TM-I. Zero bias conductance (dI/dV)v=(0), which is directly proportional to the local surface density of states at the Fermi level, shows a single distribution at temperatures T < 200 K suggesting a homogeneous electronic phase at low temperatures. In a narrow temperature window of 200 K < T < TM-I, however, an inhomogeneous distribution of (dI/dV)v=(0) has been observed. This result gives evidence for phase separation in the transition region in this compound.

Observations on the first steps of atmospheric particle formation and growth

Atmospheric aerosol particles have a significant impact on air quality, human health and global climate. The climatic effects of secondary aerosol are currently among the largest uncertainties limiting the scientific understanding of future and past climate changes. To better estimate the climatic importance of secondary aerosol particles, detailed information on atmospheric particle formation mechanisms and the vapours forming the aerosol is required. In this thesis we studied these issues by applying novel instrumentation in a boreal forest to obtain direct information on the very first steps of atmospheric nucleation and particle growth. Additionally, we used detailed laboratory experiments and process modelling to determine condensational growth properties, such as saturation vapour pressures, of dicarboxylic acids, which are organic acids often found in atmospheric samples. Based on our studies, we came to four main conclusions: 1) In the boreal forest region, both sulphurous compounds and organics are needed for secondary particle formation, the previous contributing mainly to particle formation and latter to growth; 2) A persistent pool of molecular clusters, both neutral and charged, is present and participates in atmospheric nucleation processes in boreal forests; 3) Neutral particle formation seems to dominate over ion-mediated mechanisms, at least in the boreal forest boundary layer; 4) The subcooled liquid phase saturation vapour pressures of C3-C9 dicarboxylic acids are of the order of 1e-5 1e-3 Pa at atmospheric temperatures, indicating that a mixed pre-existing particulate phase is required for their condensation in atmospheric conditions. The work presented in this thesis gives tools to better quantify the aerosol source provided by secondary aerosol formation. The results are particularly useful when estimating, for instance, anthropogenic versus biogenic influences and the fractions of secondary aerosol formation explained by neutral or ion-mediated nucleation mechanisms, at least in environments where the average particle formation rates are of the order of some tens of particles per cubic centimeter or lower. However, as the factors driving secondary particle formation are likely to vary depending on the environment, measurements on atmospheric nucleation and particle growth are needed from around the world to be able to better describe the secondary particle formation, and assess its climatic effects on a global scale.

Scanning Tunneling Spectroscopy on Pr0.68Pb0.32MnO3 single crystals

Scanning tunneling microscopy/spectroscopy studies were carried out on single crystals of colossal magnetoresistive manganite Pr0. 68Pb0.32MnO3 at different temperatures in order to probe their spatial homogeneity across the metal-insulator transition temperature TM-I(similar to 255 K). A metallic behavior of the local conductance was observed for temperatures T < TM-I. Zero bias conductance (dI/dV)v=(0), which is directly proportional to the local surface density of states at the Fermi level, shows a single distribution at temperatures T < 200 K suggesting a homogeneous electronic phase at low temperatures. In a narrow temperature window of 200 K < T < TM-I, however, an inhomogeneous distribution of (dI/dV)v=(0) has been observed. This result gives evidence for phase separation in the transition region in this compound.

Ethylation of benzene: A statistical study

A central composite rotatable experimental design was constructed for a statistical study of the ethylation of benzene in the liquid phase, with aluminum chloride catalyst, in an agitated tank system. The conversion of benzene and ethylene and the yield of monoethyl- and diethylbenzene are characterized by the response surface technique. In the experimental range studied, agitation rate has no significant effect. Catalyst concentration, rate of ethylene Flow, and temperature are the influential factors. The response surfaces may be adequately approximated by planes.

Levitation effect in zeolites: Quasielastic neutron scattering and molecular dynamics study of pentane isomers in zeolite NaY

We report the quasielastic neutron scattering (QENS) and molecular dynamics (MD) investigations into diffusion of pentane isomers in zeolite NaY. The molecular cross section perpendicular to the long molecular axis varies for the three isomers while the mass and the isomer-zeolite interaction remains essentially unchanged. Both QENS and MD results show that the branched isomers neopentane and isopentane have higher self-diffusivities as compared with n-pentane at 300 K in NaY zeolite. This result provides direct experimental evidence for the existence of nonmonotonic, anomalous dependence of self-diffusivity on molecular diameter known as the levitation effect. The energetic barrier at the bottleneck derived from MD simulations exists for n-pentane which lies in the linear regime while no such barrier is seen for neopentane which is located clearly in the anomalous regime.Activation energy is in the order E-a(n-pentane)>E-a(isopentane)>E-a(neopentane) consistent with the predictions of the levitation effect. In the liquid phase, it is seen thatD(n pentane)>D(isopentane)>D(neopentane) and E-a(n-pentane)< E-a(isopentane)< E-a(neopentane). Intermediate scattering function for small wavenumbers obtained from MD follows a single exponential decay for neopentane and isopentane. For n-pentane, a single exponential fit provides a poor fit especially at short times. Cage residence time is largest for n-pentane and lowest for neopentane. For neopentane, the width of the self-part of the dynamic structure factor shows a near monotonic decrease with wavenumber. For n-pentane a minimum is seen near k=0.5 A degrees(-1) suggesting a slowing down of motion around the 12-ring window, the bottleneck for diffusion. Finally, the result that the branched isomer has a higher diffusivity as compared with the linear analog is at variation from what is normally seen.

Raman spectrum of dimethyl sulfoxide (DMSO) and the influence of solvents

The Raman spectrum of DMSO is recorded with a Hilger two-prism spectrograph andλ 4358 Å excitation. In addition to all the Raman lines reported earlier, six new lines at 898, 925, 1223, 1309, 2811 and 2871 cm.−1 are observed and tentative assignments are given. The influence of solvents (CCl4, CHCl3, CH3COOH) on the S=O bond is also studied. A shift from the liquid phase value,i.e., 1043 cm.−1 to 1054, 1052 and 1009 cm.−1 in the respective solvents is observed. The possibilities of association effects and hydrogen bonding are discussed.

Deformation and crystallization of Zr-based amorphous alloys in homogeneous flow regime

The purpose of this study is to experimentally investigate the interaction of inelastic deformation and microstructural changes of two Zr-based bulk metallic glasses (BMGs): Zr41.25Ti13.75Cu12.5Ni10Be22.5 (commercially designated as Vitreloy 1 or Vit1) and Zr46.75Ti8.25Cu7.5Ni10Be27.5 (Vitreloy 4, Vit4). High-temperature uniaxial compression tests were performed on the two Zr alloys at various strain rates, followed by structural characterization using differential scanning calorimetry (DSC) and transmission electron microscopy (TEM). Two distinct modes of mechanically induced atomic disordering in the two alloys were observed, with Vit1 featuring clear phase separation and crystallization after deformation as observed with TEM, while Vit4 showing only structural relaxation with no crystallization. The influence of the structural changes on the mechanical behaviors of the two materials was further investigated by jump-in-strain-rate tests, and flow softening was observed in Vit4. A free volume theory was applied to explain the deformation behaviors, and the activation volumes were calculated for both alloys.

Nonclassical rotational inertia in a two-dimensional bosonic solid containing grain boundaries

We study the occurrence of nonclassical rotational inertia (NCRI) arising from superfluidity along grain boundaries in a two-dimensionalbosonic system. We make use of a standard mapping between the zero-temperature properties of this system and the statistical mechanics of interacting vortex lines in the mixed phase of a type-II superconductor. In the mapping, the liquid phase of the vortex system corresponds to the superfluid bosonic phase. We consider numerically obtained polycrystalline configurations of the vortex lines in which the microcrystals are separated by liquidlike grain-boundary regions which widen as the vortex system temperature increases. The NCRI of the corresponding zero-temperature bosonic systems can then be numerically evaluated by solving the equations of superfluid hydrodynamics in the channels near the grain boundaries. We find that the NCRI increases very abruptly as the liquid regions in the vortex system (equivalently, superfluid regions in the bosonic system) form a connected, system-spanning structure with one or more closed loops. The implications of these results for experimentally observed supersolid phenomena are discussed.

Polymeereillä stabiloitu amorfinen formulaatio

Nowadays growing number of new active pharmaceutical ingredients (API) have large molecular weight and are hydrophobic. The energy of their crystal lattice is bigger and polarity has decreased. This leads to weakened solubility and dissolution rate of the drug. These properties can be enhanced for example by amorphization. Amorphous form has the best dissolution rate in the solid state. In the amorphous form drug molecules are randomly arranged, so the energy required to dissolve molecules is lower compared to the crystalline counterpart. The disadvantage of amorphous form is that it is unstable. Amorphous form tends to crystallize. Stability of amorphous form can be enhanced by adding an adjuvant to drug product. Adjuvant is usually a polymer. Polymers prevent crystallization both by forming bonds with API molecules and by steric hindrance. The key thing in stabilizing amorphous form is good miscibility between API and polymer. They have to be mixed in a molecular level so that the polymer is able to prevent crystallization. The aim of this work was to study miscibility of drug and polymer and stability of their dispersion with different analytical methods. Amorphous dispersions were made by rotary evaporator and freeze dryer. Amorphicity was confirmed with X-ray powder diffraction (XRPD) right after preparation. Itraconazole and theophylline were the chosen molecules to be stabilized. Itraconazole was expected to be easier and theophylline more difficult to stabilize. Itraconazole was stabilized with HPMC and theophylline was stabilized with PVP. Miscibility was studied with XRPD and differential scanning calorimetry (DSC). In addition it was studied with polarized light microscope if miscibility was possible to see visually. Dispersions were kept in stressed conditions and the crystallization was analyzed with XRPD. Stability was also examined with isothermal microcalorimetry (IMC). The dispersion of itraconazole and theophylline 40/60 (w/w) was completely miscible. It was proved by linear combination of XRPD results and single glass transition temperature in DSC. Homogenic well mixed film was observed with light microscope. Phase separation was observed with other compositions. Dispersions of theophylline and PVP mixed only partly. Stability of itraconazole dispersions were better than theophylline dispersions which were mixed poorer. So miscibility was important thing considering stability. The results from isothermal microcalorimetry were similar to results from conventional stability studies. Complementary analytical methods should be used when studying miscibility so that the results are more reliable. Light microscope is one method in addition to mostly used XRPD and DSC. Analyzing light microscope photos is quite subjective but it gives an idea of miscibility. Isothermal microcalorimetry can be one option for conventional stability studies. If right conditions can be made where the crystallization is not too fast, it may be possible to predict stability with isothermal microcalorimetry.